Curable composition and methods for improving recovery properties and creep properties

ABSTRACT

Disclosed are a curable composition characterized by using a curable composition including an organic polymer (A1) having one or more silicon-containing functional groups capable of cross-linking by forming siloxane bonds in which the one or more silicon-containing functional groups capable of cross-linking by forming siloxane bonds are silicon-containing functional groups each having three or more hydrolyzable groups on one or more silicon atoms thereof; and a method for controlling the recovery properties, durability and creep resistance of the cured article. Herewith, the present invention provides a curable composition capable of giving a cured article excellent in recovery properties, durability and creep resistance, and a method for controlling the recovery properties, durability and creep resistance of the cured article.

The present invention relates to a curable composition containing anorganic polymer which has silicon-containing functional groups(hereinafter also referred to as “reactive silicon groups”) capable ofcross-linking by forming siloxane bonds.

BACKGROUND ART

It is known that an organic polymer having at least one reactive silicongroup in the molecule has an interesting property such that even at roomtemperature the organic polymer yields a rubber-like cured articlethrough cross-linking based on the formation of siloxane bonds involvingthe hydrolysis reaction and the like of the reactive silicon groupcaused by moisture and the like.

Among these reactive silicon group-containing polymers, polyoxyalkylenepolymers and polyisobutylene polymers have already been industriallyproduced to be widely used in applications to sealants, adhesives,coating materials and the like.

When resins for use in adhesives used as adhesives for interior panels,adhesives for exterior panels, adhesives for tiling, adhesives for stonetiling, adhesives for finishing walls and adhesives for vehicle panelsand the like are poor in recovery properties and creep resistance, theadhesive layers are distorted with time due to the weights of theadherends and external stress to shift the positions of panels, tilesand stone pieces as the case may be. Accordingly, the compositions to beused in these adhesives are required to be excellent in recoveryproperties and creep resistance.

Sealants are generally used for the purpose of imparting water tightnessand air tightness by filling these materials in the joints and gapsbetween various members. Accordingly, because the long termfollowability to the portions to which these adhesives are used isextremely important, the physical properties of the cured articles ofthese adhesives are required to be excellent both in recovery propertiesand in durability. Particularly, excellent recovery properties anddurability are required for compositions to be used for sealants forworking joints in buildings with large joint variation (coping,periphery of window glass, periphery of window frame/window sash,curtain wall, various exterior panels).

On the other hand, there have been disclosed room temperature-curablecompositions which have as an indispensable component an organic polymercontaining the one or more reactive silicon groups having threehydrolyzable groups bonded to the silicon atom thereof (for example,see); however, in these prior arts, descriptions are mainly made on thefast curability based on the reactive silicon group having threehydrolyzable groups bonded thereto, and there has been made nodescription to suggest the recovery properties, creep resistance anddurability.

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DISCLOSURE OF THE INVENTION

In view of the above described circumstances, the present inventiontakes as an object thereof the provision of a curable compositioncapable of giving a cured article excellent in recovery properties,durability and creep resistance. Additionally, the present inventiontakes as another object thereof the provision of an adhesive for panelor a sealant for working joint in building improved in recoveryproperties, durability and creep resistance. Moreover, the presentinvention takes as another object thereof the provision of a method forcontrolling the recovery properties, durability and creep resistance ofa cured article.

As a result of a diligent investigation to solve such problems asdescribed above, the present inventors completed the present inventionby discovering that the recovery properties, durability and creepresistance are improved by use of silicon-containing functional groupshaving three or more hydrolyzable groups on the one or more siliconatoms thereof as the reactive silicon groups in the composition.

More specifically, a first aspect of the present invention relates to acurable composition characterized by comprising: an organic polymer (A1)having one or more silicon-containing functional groups capable ofcross-linking by forming siloxane bonds in which the one or moresilicon-containing functional groups capable of cross-linking by formingsiloxane bonds are silicon-containing functional groups each havingthree or more hydrolyzable groups on one or more silicon atoms thereof;and a silicate (B).

A preferred embodiment relates to the curable composition according tothe above description, characterized in that the silicate is acondensate of a tetraalkoxysilane.

A further preferred embodiment is the curable composition according toany one of the above descriptions, characterized by further comprising atin carboxylate (C).

A second aspect of the present invention relates to a curablecomposition characterized by comprising: an organic polymer (A1) havingone or more silicon-containing functional groups capable ofcross-linking by forming siloxane bonds in which the one or moresilicon-containing functional groups capable of cross-linking by formingsiloxane bonds are silicon-containing functional groups each havingthree or more hydrolyzable groups on one or more silicon atoms thereof;and a tin carboxylate (C1) in which the α-carbon of the carboxyl groupis a quaternary carbon atom.

A third aspect of the present invention relates to a curable compositioncharacterized by comprising: an organic polymer (A1) having one or moresilicon-containing functional groups capable of cross-linking by formingsiloxane bonds in which the one or more silicon-containing functionalgroups capable of cross-linking by forming siloxane bonds aresilicon-containing functional groups each having three or morehydrolyzable groups on one or more silicon atoms thereof; a tincarboxylate (C); and an organotin catalyst (D).

A fourth aspect of the present invention relates to a curablecomposition being characterized by comprising: an organic polymer (A1)having one or more silicon-containing functional groups capable ofcross-linking by forming siloxane bonds in which the one or moresilicon-containing functional groups capable of cross-linking by formingsiloxane bonds are silicon-containing functional groups each havingthree or more hydrolyzable groups on one or more silicon atoms thereof;and a non-tin catalyst (E).

A preferred embodiment relates to the curable composition according tothe above description, characterized in that the non-tin catalyst is oneor more selected from a carboxylic acid, a metal carboxylate other thana tin carboxylate and an organic titanate.

A preferred embodiment relates to the curable composition according tothe above description, characterized in that the non-tin catalyst is acatalyst which contains a carboxylic acid and an amine compound.

A further preferred embodiment relates to the curable compositionaccording to any one of the above descriptions, characterized in thatthe carboxylic acid is a carboxylic acid in which the α-carbon atom ofthe carboxyl group is a quaternary carbon atom.

A fifth aspect of the present invention relates to a curable compositioncharacterized by comprising: an organic polymer (A1) having one or moresilicon-containing functional groups capable of cross-linking by formingsiloxane bonds in which the one or more silicon-containing functionalgroups capable of cross-linking by forming siloxane bonds aresilicon-containing functional groups each having three or morehydrolyzable groups on one or more silicon atoms thereof; and amicroballoon (F).

A sixth aspect of the present invention relates to a curable compositioncharacterized by comprising: an organic polymer (A1) having one or moresilicon-containing functional groups capable of cross-linking by formingsiloxane bonds in which the one or more silicon-containing functionalgroups capable of cross-linking by forming siloxane bonds aresilicon-containing functional groups each having three or morehydrolyzable groups on one or more silicon atoms thereof, and theproportion of the organic polymer in the total amount of the curablecomposition being 5 to 28 wt %.

A preferred embodiment relates to the curable composition according toany one of the above descriptions, characterized in that the organicpolymer having one or more silicon-containing functional groups capableof cross-linking by forming siloxane bonds is an organic polymerobtained by an addition reaction between an organic polymer having oneor more unsaturated groups introduced into the terminals thereof and ahydrosilane compound represented by the general formula (1):H—SiX₃  (1)where X represents a hydroxy group or a hydrolyzable group, and threeX's may be the same or different.

A further preferred embodiment relates to the curable compositionaccording to any one of the above descriptions, characterized in thatthe one or more silicon-containing functional groups capable ofcross-linking by forming siloxane bonds each are a trimethoxysilyl groupor a triethoxysilyl group.

A further preferred embodiment relates to the curable compositionaccording to any one of the above descriptions, characterized in thatthe one or more silicon-containing functional groups capable ofcross-linking by forming siloxane bonds each are a group represented bythe general formula (2):—Si(OR¹)₃  (2)where three R¹s each are independently a monovalent organic group having2 to 20 carbon atoms.

A seventh aspect of the present invention relates to a curablecomposition characterized by comprising: an organic polymer (A2) havingone or more silicon-containing functional groups capable ofcross-linking by forming siloxane bonds in which the one or moresilicon-containing functional groups capable of cross-linking by formingsiloxane bonds are represented by the general formula (2):—Si(OR¹)₃  (2)where R¹s are the same as described above; and an aminosilane couplingagent (G) having a group represented by the general formula (3):—SiR² _(a)(OR³)_(3-a)  (3)where a R²s each are independently a monovalent organic group having 1to 20 carbon atoms, (3-a) R³s each are independently a monovalentorganic group having 2 to 20 carbon atoms, and a represents 0, 1 or 2.

An eighth aspect of the present invention relates to a curablecomposition characterized in that the curable composition is obtained byaging a composition comprising: an organic polymer (A2) having one ormore silicon-containing functional groups capable of cross-linking byforming siloxane bonds in which the one or more silicon-containingfunctional groups capable of cross-linking by forming siloxane bonds arerepresented by the general formula (2):—Si(OR¹)₃  (2)where R¹s are the same as described above; and an aminosilane couplingagent (H) having a group represented by the general formula (4):—SiR⁴ _(b)(OCH₃)_(c)(OR⁵)_(3-b-c)  (4)where b R⁴ s each are independently a monovalent organic group having 1to 20 carbon atoms, (3-b-c) R⁵s each are independently a monovalentorganic group having 2 to 20 carbon atoms, b represents 0, 1 or 2, and crepresents 1, 2 or 3; the relation, 3-b-c≧0, is to be satisfied.

A ninth aspect of the present invention relates to a curable compositioncharacterized by comprising: an organic polymer (A2) having one or moresilicon-containing functional groups capable of cross-linking by formingsiloxane bonds in which the one or more silicon-containing functionalgroups capable of cross-linking by forming siloxane bonds arerepresented by the general formula (2):—Si(OR¹)₃  (2)where R¹s are the same as described above; and an epoxy resin (I).

A tenth aspect of the present invention relates to a curable compositioncharacterized by comprising: a polyoxyalkylene polymer (A3) having oneor more silicon-containing functional groups capable of cross-linking byforming siloxane bonds in which the one or more silicon-containingfunctional groups capable of cross-linking by forming siloxane bonds arerepresented by the general formula (2):—Si(OR¹)₃  (2)where R¹s are the same as described above; and a (meth)acrylatecopolymer (A4) having one or more silicon-containing functional groupscapable of cross-linking by forming siloxane bonds.

A preferred embodiment relates to the curable composition according tothe above description, characterized in that the one or moresilicon-containing functional groups of the (meth)acrylate copolymer arethe groups represented by the general formula (2):—Si(OR¹)₃  (2)where R¹s are the same as described above.

An eleventh aspect of the present invention relates to a curablecomposition characterized by comprising: a saturated hydrocarbon polymer(A5) having one or more silicon-containing functional groups capable ofcross-linking by forming siloxane bonds in which the one or moresilicon-containing functional groups capable of cross-linking by formingsiloxane bonds are represented by the general formula (2):—Si(OR¹)₃  (2)where R¹s are the same as described above.

A twelfth aspect of the present invention relates to a curablecomposition characterized by comprising: a meth(acrylate) copolymer (A6)having one or more silicon-containing functional groups capable ofcross-linking by forming siloxane bonds in which the one or moresilicon-containing functional groups capable of cross-linking by formingsiloxane bonds are represented by the general formula (2):—Si(OR¹)₃  (2)where R¹s are the same as described above.

A preferred embodiment relates to the curable composition according toany one of the above descriptions, characterized in that the organicpolymer having one or more silicon-containing functional groups capableof cross-linking by forming siloxane bonds is an organic polymerobtained by an addition reaction between an organic polymer having oneor more unsaturated groups introduced into the terminals thereof and ahydrosilane compound represented by the general formula (5):H—Si(OR¹)₃  (5)where R¹s are the same as described above.

A further preferred embodiment relates to the curable compositionaccording to any one of the above descriptions, characterized in thatthe organic polymer having one or more silicon-containing functionalgroups capable of cross-linking by forming siloxane bonds is an organicpolymer which substantially does not contain an amide segment (—NH—CO—)in the main chain skeleton thereof.

A further preferred embodiment relates to the curable compositionaccording to any one of the above descriptions, characterized in thatthe one or more silicon-containing functional groups capable ofcross-linking by forming siloxane bonds each are a triethoxysilyl group.

A further preferred embodiment relates to the curable compositionaccording to any one of the above descriptions, characterized by furthercomprising an aminosilane coupling agent.

A further preferred embodiment relates to a one-part curable compositionaccording to any one of the above descriptions, characterized by furthercomprising a dehydrating agent.

A thirteenth aspect of the present invention relates to a method forproducing an organic polymer having a group represented by the generalformula (6):—Si(OCH₃)_(d)(OR¹)_(3-d)  (6)where (3-d) R¹s each are independently a monovalent organic group having2 to 20 carbon atoms, and d represents 1, 2 or 3, characterized in thatan organic polymer (A2) having one or more silicon-containing functionalgroups capable of cross-linking by forming siloxane bonds in which theone or more silicon-containing functional groups capable ofcross-linking by forming siloxane bonds represented by the generalformula (2):—Si(OR¹)₃  (2)where R¹s are the same as described above, is made to undergo esterexchange reaction with a compound (J) having at least one methoxy groupcapable of undergoing ester exchange reaction.

A fourteenth aspect of the present invention relates to an adhesive forpanel, characterized in that the adhesive comprises an organic polymer(A) having one or more silicon-containing functional groups capable ofcross-linking by forming siloxane bonds; and a silicate (B).

A fifteenth aspect of the present invention relates to an adhesive forpanel characterized by comprising an organic polymer (A1) having one ormore silicon-containing functional groups in which the one or moresilicon-containing functional groups capable of cross-linking by formingsiloxane bonds are silicon-containing functional groups each havingthree or more hydrolyzable groups on one or more silicon atoms thereof.

A preferred embodiment relates to the adhesive for panel according tothe above description, characterized by using a curable composition inwhich the main chain of the organic polymer (A1) having one or moresilicon-containing functional groups capable of cross-linking by formingsiloxane bonds is a (meth)acrylate copolymer produced by a livingradical polymerization method.

A further preferred embodiment relates to the adhesive for panelaccording to any one of the above descriptions, characterized by furthercomprising a silicate (B).

A further preferred embodiment relates to the adhesive for panelaccording to any one of the above descriptions, characterized by furthercomprising a tin carboxylate (C).

A further preferred embodiment relates to the adhesive for panelaccording to any one of the above descriptions, characterized by furthercomprising an organotin catalyst (D).

A sixteenth aspect of the present invention relates to an adhesive forpanel characterized in that an organic polymer having one or moresilicon-containing functional groups capable of cross-linking by formingsiloxane bonds is an organic polymer (A7) which has on average 1.7 to 5silicon-containing functional groups capable of cross-linking by formingsiloxane bonds per molecule.

A preferred embodiment relates to the adhesive for panel according tothe above description, characterized in that the one or moresilicon-containing functional groups capable of cross-linking by formingsiloxane bonds each are a silicon-containing functional group havingthree or more hydrolyzable groups on the one or more silicon atomsthereof.

A further preferred embodiment relates to the adhesive for panelaccording to any one of the above descriptions, characterized in thatthe organic polymer having one or more silicon-containing functionalgroups capable of cross-linking by forming siloxane bonds is an organicpolymer obtained by an addition reaction between an organic polymerhaving one or more unsaturated groups introduced into the terminalsthereof and a hydrosilane compound represented by the general formula(7):H—(SiR⁶ _(2-f)X_(f)O)_(m)—SiR⁷ _(3-e)X_(e)  (7)where R⁶ and R⁷ may be the same or different, and each are an alkylgroup having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbonatoms, an aralkyl group having 7 to 20 carbon atoms, or atriorganosiloxy group represented by (R′)₃SiO—; when two or more R⁶ orR⁷ are present, they may be the same or different; here, R′ represents amonovalent hydrocarbon group having 1 to 20 carbon atoms, and three R'smay be the same or different; X represents a hydroxy group or ahydrolyzable group; when two or more X's are present, they may be thesame or different; e represents 0, 1, 2 or 3; f represents 0, 1 or 2;f's in m (SiR⁶ _(2-f)X_(f)O) groups may be the same or different; mrepresents an integer of 0 to 19; and the relation, e+Σf≧1, is to besatisfied.

A further preferred embodiment relates to the adhesive for panelaccording to any one of the above descriptions, characterized in thatthe organic polymer having one or more silicon-containing functionalgroups capable of cross-linking by forming siloxane bonds is an organicpolymer obtained by an addition reaction between an organic polymerhaving one or more unsaturated groups introduced into the terminalsthereof and a hydrosilane compound represented by the general formula(1):H—SiX₃  (1)where X's are the same as described above.

A seventeenth aspect of the present invention relates to an adhesive forpanel characterized in that an organic polymer having one or moresilicon-containing functional groups capable of cross-linking by formingsiloxane bonds is an organic polymer (A8) having a structural moietyrepresented by the general formula (8):—O—R⁸—CH(CH₃)—CH₂—(SiR⁶ _(2-f)X_(f)O)_(m)—SiR⁷ _(3-e)X_(e)  (8)where R⁸ represents a divalent organic group having 1 to 20 carbon atomsand containing as constituent atoms one or more selected from the groupconsisting of hydrogen, oxygen and nitrogen; and R⁶, R⁷, X, e, f and mare the same as described above.

A further preferred embodiment relates to the adhesive for panelaccording to the above description, characterized in that the organicpolymer having one or more silicon-containing functional groups capableof cross-linking by forming siloxane bonds is an organic polymerobtained by an addition reaction between an organic polymer having oneor more unsaturated groups introduced thereinto, represented by thegeneral formula (9):—O—R⁸—C(CH₃)═CH₂  (9)where R⁸ is the same as described above and a hydrosilane compoundrepresented by the general formula (7):H—(SiR⁶ _(2-f)X_(f)O)_(m)—SiR⁷ _(3-e)X_(e)  (7)where R⁶, R⁷, X, e, f and m are the same as described above.

A further preferred embodiment relates to the adhesive for panelaccording to any one of the above descriptions, characterized in thatthe organic polymer having one or more silicon-containing functionalgroups capable of cross-linking by forming siloxane bonds is an organicpolymer having a structural moiety represented by the general formula(10):—O—R⁸—CH(CH₃)—CH₂—SiX₃  (10)where R⁸ and X's are the same as described above.

A further preferred embodiment relates to the adhesive for panelaccording to any one of the above descriptions, characterized in thatthe organic polymer having one or more silicon-containing functionalgroups capable of cross-linking by forming siloxane bonds is an organicpolymer which substantially does not contain an amide segment (—NH—CO—)in the main chain skeleton thereof.

A further preferred embodiment relates to the adhesive for panelaccording to any one of the above descriptions, characterized in thatthe one or more silicon-containing functional groups capable ofcross-linking by forming siloxane bonds each are a group represented bythe general formula (2):—Si(OR¹)₃  (2)where R¹s are the same as described above.

A further preferred embodiment relates to the adhesive for panelaccording to any one of the above descriptions, characterized in thatthe one or more silicon-containing functional groups capable ofcross-linking by forming siloxane bonds each are a triethoxysilyl group.

An eighteenth aspect of the present invention relates to a sealant forworking joint in building, characterized in that the sealant comprisesan organic polymer (A) which has one or more silicon-containingfunctional groups capable of cross-linking by forming siloxane bonds;and a silicate (B).

A nineteenth aspect of the present invention relates to a sealant forworking joint in building characterized by comprising an organic polymer(A1) having one or more silicon-containing functional groups capable ofcross-linking by forming siloxane bonds in which the one or moresilicon-containing functional groups capable of cross-linking by formingsiloxane bonds each are a silicon-containing functional group havingthree or more hydrolyzable groups on the one or more silicon atomsthereof.

A preferred embodiment relates to the sealant for working joint inbuilding according to the above description, characterized by using acurable composition in which the main chain of the organic polymer (A1)having one or more silicon-containing functional groups capable ofcross-linking by forming siloxane bonds is a (meth)acrylate copolymerproduced by a living radical polymerization method.

A further preferred embodiment relates to the sealant for working jointin building according to any one of the above descriptions,characterized by further comprising a silicate (B).

A further preferred embodiment relates to the sealant for working jointin building according to any one of the above descriptions,characterized by further comprising a tin carboxylate (C).

A further preferred embodiment relates to the sealant for working jointin building according to any one of the above descriptions,characterized by further comprising an organotin catalyst (D).

A twentieth aspect of the present invention relates to a sealant forworking joint in building characterized in that an organic polymerhaving one or more silicon-containing functional groups capable ofcross-linking by forming siloxane bonds is an organic polymer (A7) whichhas on average 1.7 to 5 silicon-containing functional groups capable ofcross-linking by forming siloxane bonds per molecule.

A preferred embodiment relates to the sealant for working joint inbuilding according to the above description, characterized in that theone or more silicon-containing functional groups capable ofcross-linking by forming siloxane bonds each are a silicon-containingfunctional group having three or more hydrolyzable groups on the one ormore silicon atoms thereof.

A further preferred embodiment relates to the sealant for working jointin building according to any one of the above descriptions,characterized in that the organic polymer having one or moresilicon-containing functional groups capable of cross-linking by formingsiloxane bonds is an organic polymer obtained by an addition reactionbetween an organic polymer having one or more unsaturated groupsintroduced into the terminals thereof and a hydrosilane compoundrepresented by the general formula (7):H—(SiR⁶ _(2-f)X_(f)O)_(m)—SiR⁷ _(3-e)X_(e)  (7)where R⁶ and R⁷ may be the same or different, and each are an alkylgroup having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbonatoms, an aralkyl group having 7 to 20 carbon atoms, or atriorganosiloxy group represented by (R′)₃SiO—; when two or more R⁶ orR⁷ are present, they may be the same or different; here, R′ represents amonovalent hydrocarbon group having 1 to 20 carbon atoms, and three R'smay be the same or different; X represents a hydroxy group or ahydrolyzable group; when two or more X's are present, they may be thesame or different; e represents 0, 1, 2 or 3; f represents 0, 1 or 2;f's in m (SiR⁶ _(2-f)X_(f)O) groups may be the same or different; mrepresents an integer of 0 to 19; and the relation, e+Σf≧1, is to besatisfied.

A further preferred embodiment relates to the sealant for working jointin building according to any one of the above descriptions,characterized in that the organic polymer having one or moresilicon-containing functional groups capable of cross-linking by formingsiloxane bonds is an organic polymer obtained by an addition reactionbetween an organic polymer having one or more unsaturated groupsintroduced into the terminals thereof and a hydrosilane compoundrepresented by the general formula (1):H—SiX₃  (1)where X's are the same as described above.

A twenty-first aspect of the present invention relates to a sealant forworking joint in building characterized in that an organic polymerhaving one or more silicon-containing functional groups capable ofcross-linking by forming siloxane bonds is an organic polymer (A8)having a structural moiety represented by the general formula (8):

—O—R⁸—CH(CH₃)—CH₂—(SiR⁶ _(2-f)X_(f)O)_(m)—SiR⁷ _(3-e)X_(e)  (8)

where R⁸ represents a divalent organic group having 1 to 20 carbon atomsand containing as constituent atoms one or more selected from the groupconsisting of hydrogen, oxygen and nitrogen; and R⁶, R⁷, X, e, f and mare the same as described above.

A preferred embodiment relates to the sealant for working joint inbuilding according to the above description, characterized in that theorganic polymer having one or more silicon-containing functional groupscapable of cross-linking by forming siloxane bonds is an organic polymerobtained by an addition reaction between an organic polymer having oneor more unsaturated groups introduced thereinto, represented by thegeneral formula (9):—O—R⁸—C(CH₃)═CH₂  (9)where R⁸ is the same as described above, and a hydrosilane compoundrepresented by the general formula (7):H—(SiR⁶ _(2-f)X_(f)O)_(m)—SiR⁷ _(3-e)X_(e)  (7)where R⁶, R⁷, X, e, f and m are the same as described above.

A further preferred embodiment relates to the sealant for working jointin building according to any one of the above descriptions,characterized in that the organic polymer having one or moresilicon-containing functional groups capable of cross-linking by formingsiloxane bonds is an organic polymer having a structural moietyrepresented by the general formula (10):—O—R⁸—CH(CH₃)—CH₂—SiX₃  (10)where R⁸ and X's are the same as described above.

A further preferred embodiment relates to the sealant for working jointin building according to any one of the above descriptions,characterized in that the organic polymer having one or moresilicon-containing functional groups capable of cross-linking by formingsiloxane bonds is an organic polymer which substantially does notcontain an amide segment (—NH—CO—) in the main chain skeleton thereof.

A further preferred embodiment relates to the sealant for working jointin building according to any one of the above descriptions,characterized in that the one or more silicon-containing functionalgroups capable of cross-linking by forming siloxane bonds each are agroup represented by the general formula (2):—Si(OR¹)₃  (2)where R¹s are the same as described above.

A further preferred embodiment relates to the sealant for working jointin building according to any one of the above descriptions,characterized in that the one or more silicon-containing functionalgroups capable of cross-linking by forming siloxane bonds each are atriethoxysilyl group.

A twenty-second aspect of the present invention relates to a method forcontrolling the recovery properties, durability and creep resistance ofa cured article, characterized by using a curable composition whichcontains an organic polymer (A) having one or more silicon-containingfunctional groups capable of cross-linking by forming siloxane bonds;and a silicate (B).

A twenty-third aspect of the present invention relates to a method forcontrolling the recovery properties, durability and creep resistance ofa cured article, characterized by using a curable composition comprisingan organic polymer (A1) having one or more silicon-containing functionalgroups capable of cross-linking by forming siloxane bonds in which oneor more silicon-containing functional groups capable of cross-linking byforming siloxane bonds each are a silicon-containing functional grouphaving three or more hydrolyzable groups on the one or more siliconatoms thereof.

A preferred embodiment relates to the method for controlling therecovery properties, durability and creep resistance of a cured articleaccording to the above description, characterized by using a curablecomposition in which the main chain of the organic polymer (A1) havingone or more silicon-containing functional groups capable ofcross-linking by forming siloxane bonds is a (meth)acrylate copolymerproduced by a living radical polymerization method.

A further preferred embodiment relates to the method for controlling therecovery properties, durability and creep resistance of a cured articleaccording to any one of the above descriptions, characterized by using acurable composition further comprising a silicate (B).

A further preferred embodiment relates to the method for controlling therecovery properties, durability and creep resistance of a cured articleaccording to any one of the above descriptions, characterized by using acurable composition further comprising a tin carboxylate (C).

A further preferred embodiment relates to the method for controlling therecovery properties, durability and creep resistance of a cured articleaccording to any one of the above descriptions, characterized by using acurable composition further comprising an organotin catalyst (D).

A twenty-fourth aspect of the present invention relates to a method forcontrolling the recovery properties, durability and creep resistance ofa cured article characterized by using a curable composition in which anorganic polymer having one or more silicon-containing functional groupscapable of cross-linking by forming siloxane bonds is an organic polymer(A7) which has on average 1.7 to 5 silicon-containing functional groupscapable of cross-linking by forming siloxane bonds per molecule.

A preferred embodiment relates to the method for controlling therecovery properties, durability and creep resistance of a cured articleaccording to the above description, characterized by using a curablecomposition in which the one or more silicon-containing functionalgroups capable of cross-linking by forming siloxane bonds aresilicon-containing functional groups each having three or morehydrolyzable groups on one or more silicon atoms thereof.

A further preferred embodiment relates to the method for controlling therecovery properties, durability and creep resistance of a cured articleaccording to any one of the above descriptions, characterized by using acurable composition in which the organic polymer having one or moresilicon-containing functional groups capable of cross-linking by formingsiloxane bonds is an organic polymer obtained by an addition reactionbetween an organic polymer having one or more unsaturated groupsintroduced into the terminals thereof and a hydrosilane compoundrepresented by the general formula (7):H—(SiR⁶ _(2-f)X_(f)O)_(m)—SiR⁷ _(3-e)X_(e)  (7)where R⁶, R⁷, X, e, f and m are the same as described above.

A further preferred embodiment relates to the method for controlling therecovery properties, durability and creep resistance of a cured articleaccording to any one of the above descriptions, characterized by using acurable composition in which the organic polymer having one or moresilicon-containing functional groups capable of cross-linking by formingsiloxane bonds is an organic polymer obtained by an addition reactionbetween an organic polymer having one or more unsaturated groupsintroduced into the terminals thereof and a hydrosilane compoundrepresented by the general formula (1):H—SiX₃  (1)where X represents a hydroxy group or a hydrolyzable group, and threeX's may be the same or different.

A twenty-fifth aspect of the present invention relates to a method forcontrolling the recovery properties, durability and creep resistance ofa cured article, characterized by using a curable composition in whichan organic polymer having one or more silicon-containing functionalgroups capable of cross-linking by forming siloxane bonds is an organicpolymer (A8) having a structural moiety represented by the generalformula (8):—O—R⁸—CH(CH₃)—CH₂—(SiR⁶ _(2-f)X_(f)O)_(m)—SiR⁷ _(3-e)X_(e)  (8)where R⁶, R⁷, R⁸, X, e, f and m are the same as described above.

A preferred embodiment relates to the method for controlling therecovery properties, durability and creep resistance of a cured articleaccording to the above description, characterized by using a curablecomposition in which the organic polymer having one or moresilicon-containing functional groups capable of cross-linking by formingsiloxane bonds is an organic polymer obtained by an addition reactionbetween an organic polymer having one or more unsaturated groupsintroduced thereinto, represented by the general formula (9):—O—R⁸—C(CH₃)═CH₂  (9)where R⁸ is the same as described above, and a hydrosilane compoundrepresented by the general formula (7):H—(SiR⁶ _(2-f)X_(f)O)_(m)—SiR⁷ _(3-e)X_(e)  (7)where R⁶, R⁷, X, e, f and m are the same as described above.

A further preferred embodiment relates to the method for controlling therecovery properties, durability and creep resistance of a cured articleaccording to any one of the above descriptions, characterized by using acurable composition in which the organic polymer having one or moresilicon-containing functional groups capable of cross-linking by formingsiloxane bonds is an organic polymer having a structural moietyrepresented by the general formula (10):—O—R⁸—CH(CH₃)—CH₂—SiX₃  (10)where R⁸ and X's are the same as described above.

A further preferred embodiment relates to the method for controlling therecovery properties, durability and creep resistance of a cured articleaccording to any one of the above descriptions, characterized by using acurable composition in which the organic polymer having one or moresilicon-containing functional groups capable of cross-linking by formingsiloxane bonds is an organic polymer which substantially does notcontain an amide segment (—NH—CO—) in the main chain skeleton thereof.

A further preferred embodiment relates to the method for controlling therecovery properties, durability and creep resistance of a cured articleaccording to any one of the above descriptions, characterized by using acurable composition in which the one or more silicon-containingfunctional groups capable of cross-linking by forming siloxane bondseach are a group represented by the general formula (2):—Si(OR¹)₃  (2)where three R¹s each are independently a monovalent organic group having2 to 20 carbon atoms.

A further preferred embodiment relates to the method for controlling therecovery properties, durability and creep resistance of a cured articleaccording to any one of the above descriptions, characterized by using acurable composition in which the one or more silicon-containingfunctional groups capable of cross-linking by forming siloxane bondseach are a triethoxysilyl group.

A twenty-sixth aspect of the present invention relates to a method forimproving thin-layer curability, characterized by using a curablecomposition comprising: an organic polymer (A1) having one or moresilicon-containing functional groups capable of cross-linking by formingsiloxane bonds in which the one or more silicon-containing functionalgroups capable of cross-linking by forming siloxane bonds aresilicon-containing functional groups each having three or morehydrolyzable groups on one or more silicon atoms thereof; and anorganotin catalyst (D).

The curable composition of the present invention is excellent inrecovery properties, durability and creep resistance.

BEST MODE FOR CARRYING OUT THE INVENTION

No particular constraint is imposed on the main chain skeleton of areactive silicon group-containing organic polymer (A) used in thepresent invention, and organic polymers having various types of mainchain skeletons can be used.

More specifically, examples of the organic polymer (A) includepolyoxyalkylene polymers such as polyoxyethylene, polyoxypropylene,polyoxybutylene, polyoxytetramethylene, polyoxyethylene-polyoxypropylenecopolymer, and polyoxypropylene-polyoxybutylene copolymer; hydrocarbonpolymers such as ethylene-propylene copolymer, polyisobutylene,copolymers between isobutylene and isoprene and the like,polychloroprene, polyisoprene, copolymers between isoprene or butadieneand acrylonitrile and/or styrene and the like, polybutadiene, copolymersbetween isoprene or butadiene and acrylonitrile, styrene and the like,hydrogenated polyolefin polymers obtained by hydrogenation of thesepolyolefin polymers; polyester polymers obtained by the condensationbetween dibasic acids such as adipic acid and glycol, or by thering-opening polymerization of lactones; (meth)acrylate polymersobtained by radical polymerization of the monomers such as ethyl(meth)acrylate and butyl (meth)acrylate; vinyl polymers obtained byradical polymerization of (meth)acrylate monomers, and the monomers suchas vinyl acetate, acrylonitrile and styrene; graft polymers obtained bypolymerization of vinyl monomers in the above described organicpolymers; polysulfide polymers; polyamide polymers such as nylon 6obtained by ring-opening polymerization of ε-caprolactam, nylon 6,6obtained by condensation polymerization between hexamethylenediamine andadipic acid, nylon 6,10 obtained by condensation polymerization betweenhexamethylenediamine and sebacic acid, nylon 11 obtained by condensationpolymerization of ε-aminoundecanoic acid, nylon 12 obtained byring-opening polymerization of ε-aminolaurolactam, and copolymerizednylons containing two or more components of the above described nylons;polycarbonate polymers manufactured by condensation polymerization of,for example, bisphenol A and carbonyl chloride; and diallyl phthalatepolymers. Among the polymers having the above described main chainskeletons, polyoxyalkylene polymers, hydrocarbon polymers, polyesterpolymers, (meth)acrylate polymers, and polycarbonate polymers arepreferable because these polymers are easily available and can be easilymanufactured.

Moreover, saturated hydrocarbon polymers such as polyisobutylene,hydrogenated polyisoprene and hydrogenated polybutadiene,polyoxyalkylene polymers, and (meth)acrylate polymers are particularlypreferable because these polymers are relatively low in glass transitiontemperature and yield cured articles excellent in low-temperatureresistance.

The above described organic polymer (A) may contain other componentssuch as a urethane bond-containing component in its main chain skeletonas long as the advantageous effects of the present invention are notgreatly impaired.

No particular constraint is imposed on the urethane-bond containingcomponent; examples of the urethane bond-containing component includethose obtained by reaction of polyisocyanate compounds, such as aromaticpolyisocyanates including toluene (tolylene) diisocyanate,diphenylmethane diisocyanate and xylylene diisocyanate, and aliphaticpolyisocyanates including isophorone diisocyanate and hexamethylenediisocyanate, with polyols having the above described various types ofmain chain skeletons.

When amide segments (—NH—CO—) generated in the main chain skeleton onthe basis of the above described urethane bond are abundant, theviscosity of the organic polymer becomes high to form a composition poorin workability. Accordingly, the amount of the amide segments occupyingthe main chain skeleton of the organic polymer is preferably 3 wt % orless, more preferably 1 wt % or less, and most preferably substantiallynull.

The reactive silicon group contained in the reactive silicongroup-containing organic polymer is a group having one or more hydroxylgroups or one or more hydrolyzable groups, which bonds to the siliconatom, and being capable of cross-linking by forming siloxane bonds by areaction accelerated by a silanol condensation catalyst. As the reactivesilicon group, there can be cited a group represented by the generalformula (11):—(SiR¹ _(2-b)X_(b)O)_(m)—SiR² _(3-a)X_(a)  (11)where R¹ and R² may be the same or different, and each are an alkylgroup having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbonatoms, an aralkyl group having 7 to 20 carbon atoms, or atriorganosiloxy group represented by (R′)₃SiO—; when two or more R¹ orR² are present, they may be the same or different; here, R′ represents amonovalent hydrocarbon group having 1 to 20 carbon atoms, and the threeR's may be the same or different; X represents a hydroxy group or ahydrolyzable group; when two or more X's are present, they may be thesame or different; a represents 0, 1, 2 or 3; b represents 0, 1 or 2; bsin m (SiR¹ _(2-b)X_(b)O) groups may be the same or different; mrepresents an integer of 0 to 19; and the relation, a+Σ≧1, is to besatisfied.

The hydrolyzable group is not particularly limited, and may be ahydrolyzable group well known in the art. More specifically, examples ofthe hydrolyzable group include a hydrogen atom, a halogen atom, analkoxy group, an acyloxy group, a ketoximate group, an amino group, anamide group, an acid amide group, an aminooxy group, a mercapto group,and an alkenyloxy group. Of these groups, a hydrogen atom, an alkoxygroup, an acyloxy group, a ketoximate group, an amino group, an amidegroup, an aminooxy group, a mercapto group and an alkenyloxy group arepreferable; an alkoxy group is particularly preferable from theviewpoints of moderate hydrolyzability and easy handlablity.

To one silicon atom, 1 to 3 hydrolyzable groups and 1 to 3 hydroxygroups can be bonded, and (a+Σb) falls preferably in the range from 1 to5. When two or more hydrolyzable groups and two or more hydroxy groupsare bonded in a reactive silicon group, the hydrolyzable groups may bethe same or different.

In particular, because of easy availability, preferable is the reactivesilicon group represented by the general formula (12):—SiR² _(3-a)X_(a)  (12)where R² and X are the same as described above, and a is an integer of 1to 3.

Additionally, specific examples of R¹ and R² in the above generalformulas (11) and (12) include alkyl groups such as a methyl group andan ethyl group; cycloalkyl groups such as a cyclohexyl group; arylgroups such as a phenyl group; aralkyl groups such as a benzyl group;and a triorganosiloxy group represented by (R′)₃SiO— in which R′ is amethyl group, a phenyl group or the like. Of these groups, a methylgroup is particularly preferable.

More specific examples of the reactive silicon group include atrimethoxysilyl group, a triethoxysilyl group, a triisopropoxysilylgroup, a dimethoxymethylsilyl group, a diethoxymethylsilyl group, and adiisopropoxymethylsilyl group.

In the present invention, a particular organic polymer, belonging to the(A) component organic polymer, which has one or more silicon-containingfunctional groups each having three or more hydrolyzable groups bondedto the one or more silicon atoms thereof (namely, a+b×m in the generalformula (11) is 3 or more) can be used as the (A1) component.

The (A1) component has three or more hydrolyzable groups bonded to theone or more silicon atoms thereof, and a cross-linked cured articlethereof obtained through the silanol condensation reaction involving thereactive silicon groups exhibits a satisfactory recovery properties, andalso exhibits marked improvement effects on the creep resistance and thedurability as compared to the case of a reactive silicongroup-containing organic polymer in which each of the reactive silicongroups has two or less hydrolyzable groups.

The value of a+b×m in the general formula (11) for the (A1) component ispreferably 3 to 5, and particularly preferably 3. Of such reactivesilicon groups, trialkoxysilyl groups are preferable because thesegroups have particularly significant improvement effects of the recoveryproperties, durability and creep resistance of the curable compositionof the present invention, and the raw materials thereof are easilyavailable. Here, the alkoxyl groups having 1 to 20 carbon atoms arepreferable, those having 1 to 10 carbon atoms are more preferable andthose having 1 to 4 carbon atoms are furthermore preferable.Specifically, a trimethoxysilyl group and a triethoxysilyl group aremost preferable. When the number of carbon atoms is larger than 20,curing is sometimes slowed.

Additionally, the (A1) component has effects of improving the waterresistant adhesion, moisture and heat resistant adhesion, and surfaceweather resistance of the curable composition of the present invention.

In general, it is known that with decreasing weight percentage of areactive silicon group-containing organic polymer in a curablecomposition, the durability of the obtained cured article is degraded.However, the use of the (A1) component of the present invention as thereactive silicon group-containing organic polymer makes it possible tomaintain a high durability even when the weight percentage of a reactivesilicon group-containing organic polymer in a curable composition ismade low. Accordingly, when the proportion of the (A1) component in acurable composition is 5 to 28 wt %, more preferably 10 to 26 wt %, andparticularly preferably 15 to 24 wt %, both low cost and high durabilitycan be preferably realized.

In the present invention, a particular organic polymer, belonging to the(A1) component organic polymer, which has a trialkoxysilyl group having2 to 20 carbon atoms, can be used as the (A2) component. Morespecifically, the organic polymer having a group represented by thegeneral formula (2) can be used as the (A2) component:—Si(OR¹)₃  (2)where three R¹s each are independently a monovalent organic group having2 to 20 carbon atoms.

It is known that methanol generated by the hydrolysis reaction of amethoxysilyl group has such a specific toxicity that it causes opticnerve disorder. On the other hand, because in the (A2) component thenumber of carbon atoms of each of the alkoxy groups bonded to thesilicon atom is 2 to 20, the alcohols generated by the hydrolysisreaction of the reactive silicon group do not include highly toxicmethanol and the (A2) component leads to a highly safe composition.

The number of the carbon atoms of R¹ in the general formula (2) for the(A2) component is more preferably 2 to 10, and particularly preferably 2to 4; in the case where the number is 2, the alcohol generated by thehydrolysis is ethanol, which is of the highest safety, so that this caseis most preferable. More specifically, the triethoxysilyl group is mostpreferable. In the case where the number of the carbon atoms is largerthan 20, sometimes the curing of the curable composition is made slow,and sometimes the anesthetic action and stimulating action due to thegenerated alcohol are significant.

Moreover, in the present invention, a particular organic polymer,belonging to the (A2) component organic polymer, in which the main chainskeleton is a polyoxyalkylene, can be used as the (A3) component. Morespecifically, the polyoxyalkylene polymer having a group represented bythe general formula (2) can be used as the (A3) component:—Si(OR¹)₃  (2)where R¹s are the same as described above.

The average number of the reactive silicon groups per molecule in theorganic polymer (A) is preferably at least 1, and more preferably 1.1 to5. When the number of the reactive silicon groups contained in onemolecule of the organic polymer (A) is less than 1, the curabilitybecomes insufficient and satisfactory rubber elasticity behavior ishardly exhibited. The reactive silicon groups may be located at theterminals or in the inner portion of the molecular chain of the organicpolymer (A). When the reactive silicon groups are located at theterminals of the molecular chain, the effective chain density in theorganic polymer (A) component contained in the finally formed curedarticle becomes large, so that it becomes easier to obtain a rubber-likecured article having a high strength, a high elongation property and alow elastic modulus.

In the present invention, a particular organic polymer, belonging to the(A) component organic polymer, in which the average number of thereactive silicon groups per molecule is 1.7 to 5 can be used as the (A7)component.

In the (A7) component, the average number of the reactive silicon groupsper molecule is 1.7 to 5; a cross-linked cured article obtainedtherefrom through the silanol condensation reaction involving thereactive silicon groups exhibits a satisfactory recovery properties, andalso exhibits marked improvement effects of the creep resistance and thedurability as compared to the case of an organic polymer in which theaverage number of the reactive silicon groups per molecule is less than1.7.

The number of the reactive silicon groups per molecule of the (A7)component is more preferably 2 to 4, and particularly preferably 2.3 to3. When the number of the reactive silicon groups per molecule is lessthan 1.7, the improvement effect of recovery properties, durability andcreep resistance of the curable composition of the present invention issometimes insufficient, while when the number of the groups concerned islarger than 5, the elongation of the obtained cured article sometimesbecomes small.

In the present invention, a particular organic polymer, belonging to the(A) component organic polymer, which has a structural moiety representedby the general formula (8) can be used as the (A8) component:—O—R⁸—CH(CH₃)—CH₂—(SiR⁶ _(2-f)X_(f)O)_(m)—SiR⁷ _(3-e)X_(e)  (8)where R⁸ represents a divalent organic group having 1 to 20 carbon atomsand containing as constituent atoms one or more selected from the groupconsisting of hydrogen, oxygen and nitrogen; and R⁶, R⁷, X, e, f and mare the same as described above.

The (A8) component has the structural moiety represented by the generalformula (8); a cross-linked cured article obtained therefrom through thesilanol condensation reaction involving the reactive silicon groupsexhibits a satisfactory recovery properties, and also exhibits markedimprovement effects of the creep resistance and the durability ascompared to the case of an organic polymer which has the terminalstructure other than that represented by the general formula (8).

The number of the carbon atoms of R⁸ in the general formula (8) ispreferably 1 to 10 from the viewpoint of availability, and particularlypreferably 1 to 4. More specifically, R³ is preferably a methylenegroup.

In the case where the (A8) component is an organic polymer having astructural moiety represented by the general formula (10):—O—R⁸—CH(CH₃)—CH₂—SiX₃  (10 )where R⁸ and X's are the same as described above, the improvementeffects of the recovery properties, durability and creep resistance ofthe curable composition of the present invention are particularlysignificant, and the raw materials thereof is easily available, andhence such an organic polymer is preferable.

The introduction of the reactive silicon group in the (A) component maybe carried out by methods well known in the art. More specifically,examples of such methods include the following:

(a) With an organic polymer having in the molecule functional groupssuch as hydroxy groups, an organic compound having both an active groupexhibiting reactivity to the functional groups and an unsaturated groupis reacted, to yield an unsaturated group-containing organic polymer.Alternatively, an unsaturated group-containing organic polymer isobtained by copolymerization of an epoxy compound having an unsaturatedgroup. Then, a reactive silicon group-containing hydrosilane is reactedwith the obtained reaction product to be hydrosilylated.

(b) With an unsaturated group-containing organic polymer, obtainedsimilarly to the method described in (a), a mercapto group-and reactivesilicon group-containing compound is reacted.

(c) With an organic polymer having in the molecule functional groupssuch as hydroxy groups, epoxy groups and isocyanate groups, a compoundhaving a functional group, exhibiting reactivity to the functionalgroups, and having a reactive silicon group is reacted.

Among the above methods, a method described in (a) or a method describedin (c) in which a hydroxy group-terminated polymer is reacted with anisocyanate group- and reactive silicon group-containing compound ispreferable because the method provides a high conversion rate for arelatively short reaction time. Additionally, the method described in(a) is particularly preferable because an organic polymer obtained bythe method described in (a) is lower in viscosity and more satisfactoryin workability than an organic polymer obtained by the method describedin (c), and an organic polymer obtained by the method described in (b)is strong in odor due to mercaptosilane.

Specific examples of the hydrosilane compound used in the methoddescribed in (a) include halogenated silanes such as trichlorosilane,methyldichlorosilane, dimethylchlorosilane and phenyldichlorosilane;alkoxysilanes such as trimethoxysilane, triethoxysilane,methyldiethoxysilane, methyldimethoxysilane and phenyldimethoxysilane;acyloxysilanes such as methyldiacetoxysilane and phenyldiacetoxysilane;and ketoximatesilanes such as bis(dimethylketoximate)methylsilane andbis(cyclohexylketoximate)methylsilane; however, the hydrosilane compoundused in the method described in (a) is not limited to these compounds.Among these examples, halogenated silanes and alkoxysilanes arepreferable; in particular, alkoxysilanes are most preferable because theobtained curable compositions are moderately hydrolyzable and easilyhandlable.

Among the above described hydrosilane compounds, the hydrosilanecompounds represented by the general formula (1) are preferable becausesignificant is the improvement effect on the recovery properties,durability and creep resistance of each of the curable compositions madeof organic polymers obtained from addition reaction of the hydrosilanecompounds concerned:H—SiX₃  (1)where X's are the same as described above. Among the hydrosilanecompounds represented by the general formula (1) , trialkoxysilanes suchas trimethoxysilane, triethoxysilane and triisopropoxysilane are morepreferable.

Among the above described trialkoxysilanes, trialkoxysilanes such astrimethoxysilane having alkoxy groups (methoxy groups) each having onecarbon atom sometimes undergoes rapidly proceeding disproportionationreaction; when the disproportionation reaction proceeds, a fairlyharmful compound such as dimethoxysilane is generated. From theviewpoint of handling safety, it is preferable to use trialkoxysilaneseach containing alkoxy groups having two or more carbon atomsrepresented by the general formula (5):H—Si(OR¹)₃  (5)where R¹s are the same as described above. Triethoxysilane is mostpreferable from the viewpoints of the availability and handling safetythereof, and from the viewpoints of the recovery properties, durabilityand creep resistance of each of the obtained curable compositions.

Examples of the synthesis method described in (b) include a method inwhich a mercapto group- and reactive silicon group-containing compoundis introduced into the sites on the unsaturated bonds of an organicpolymer by means of a radical addition reaction in the presence of aradical initiator and/or a radical generating source; however, thesynthesis method concerned is not limited to these methods. Examples ofthe above described mercapto group- and reactive silicongroup-containing compound include γ-mercaptopropyltrimethoxysilane,γ-mercaptopropylmethyldimethoxysilane, γ-mercaptopropyltriethoxysilaneand γ-mercaptopropylmethyldiethoxysilane; however, the mercapto group-and reactive silicon group-containing compound is not limited to thesecompounds.

Examples of the method, of the methods described in (c), in which ahydroxy-terminated polymer is reacted with an isocyanate group- andreactive silicon group-containing compound include a method disclosed inJapanese Patent Laid-Open No. 3-47825; however, the method concerned isnot limited to these methods. Examples of the above described isocyanategroup- and reactive silicon group-containing compound includeγ-isocyanatopropyltrimethoxysilane,γ-isocyanatopropylmethyldimethoxysilane,γ-isocyanatopropyltriethoxysilane, andγ-isocyanatopropylmethyldiethoxysilane; however, the compound concernedis not limited to these compounds.

As described above, silane compounds each having three hydrolyzablegroups bonded to one silicon atom such as trimethoxysilane sometimesundergo proceeding disproportionation reaction; particularly,trialkoxysilanes such as trimethoxysilane having alkoxy groups (methoxygroups) each having one carbon atom sometimes undergoes rapidlyproceeding disproportionation reaction. When the disproportionationreaction proceeds, a fairly harmful compound such as dimethoxysilane isgenerated. However, with γ-mercaptopropyltrimethoxysilane andγ-isocyanatopropyltrimethoxysilane, no such disproportionation reactionproceeds. Accordingly, when a trialkoxysilyl group having a methoxygroup such as trimethoxysilyl group is used as the silicon-containinggroup, it is preferable to use the synthesis methods described in (b) or(c).

As a method for obtaining an organic polymer having one or moresilicon-containing groups each with one or more silicon atoms bonded tomethoxy groups, there can be cited a method in which an organic polymer(namely, the above described (A2) component) having one or more reactivesilicon groups represented by the general formula (2) is produced bymeans of any one of the above described methods (a) (b) and (c):—Si(OR¹)₃  (2)where R¹s are the same as described above, and then the obtained organicpolymer is made to undergo ester exchange reaction with a compound (J)having at least one methoxy group capable of undergoing ester exchangereaction in the presence or absence of an ester exchange reactioncatalyst, whereby an organic polymer having one or more groupsrepresented by the general formula (6) is produced:—Si(OCH₃)_(d)(OR¹)_(3-d)  (6)where (3-d) R¹s each are independently a monovalent organic group having2 to 20 carbon atoms, and d represents 1, 2 or 3. The organic polymerhaving the groups represented by the general formula (6) exhibits afaster curability than the organic polymer having the groups representedby the general formula (2).

Among the above described production methods, more preferable is themethod in which the reactive silicon groups are introduced into anorganic polymer by means of the method (a), and then the polymerundergoes ester exchange reaction with the above described (J) componentto thereby produce an organic polymer having the groups represented bythe general formula (6), because the method concerned does not generatein the course of production a harmful compound such as dimethoxysilanedue to disproportionation reaction; and the organic polymer thusproduced is weaker in odor than the organic polymer obtained by themethod (b), and gives a curable composition lower in viscosity andbetter in workability than that based on the organic polymer obtained bythe method (c).

No particular constraint is imposed on the compound (J) having at leastone methoxy group capable of undergoing ester exchange reaction, andvarious types of compounds can be used as the compound (J).

Here, the examples of the (J) component may include methanol, methylesters of various acids such as carboxylic acids and sulfonic acids, andcompounds having silicon atoms bonded to at least one methoxy group. Asa compound having silicon atoms bonded to at least one methoxy group,more preferable is a compound having 2 to 4 methoxy groups bonded to thesame silicon atom, because such a compound has a faster rate of esterexchange reaction. Moreover, a compound having 2 to 4 methoxy groupsbonded to the same silicon atom and an amino group is particularlypreferable because of a fast rate of ester exchange reaction.

Specific examples include amino group-containing silanes such asγ-aminopropyltrimethoxysilane, γ-aminopropylmethyldimethoxysilane,γ-((β-aminoethyl)amino)propyltrimethoxysilane,γ-((β-aminoethyl)amino)propylmethyldimethoxysilane,γ-ureidopropyltrimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane,and N-benzyl-γ-aminopropyltrimethoxysilane. Additionally, thederivatives obtained by modifying the above described silane compoundsand the condensation reaction products of the above described silanecompounds can be used as the (J) component.

The above described amino group-containing silanes are preferablebecause they undergo ester exchange reaction which can proceed under theconditions of such relatively low temperatures as 60° C. or lower in thepresence of an ester exchange reaction catalyst.

As for the (J) component used in the present invention, the (J)component is used to undergo ester exchange reaction within a rangepreferably from 0.1 to 10 parts, and particularly preferably from 1 to 5parts in relation to 100 parts of the (A2) component of the reactivesilicon group-containing organic polymer. The above described (J)components may be used each alone or as admixtures of two or morethereof.

The reactive silicon group-containing organic polymer (A) may be astraight chain or may have branches, and the number average molecularweight thereof, measured by GPC relative to polystyrene standard, ispreferably of the order of 500 to 50,000, and more preferably 1,000 to30,000. When the number average molecular weight is less than 500, thereis found an adverse trend involving the elongation property, while whenthe number average molecular weight exceeds 50,000, there is found anadverse trend involving the workability because the viscosity becomeshigh.

The reactive silicon group may be located at the terminals of theorganic polymer molecule chain or in the inner portion of the chain, orboth at the terminals and in the inner portion. In particular, thereactive silicon groups located at the molecular terminals arepreferable because such groups increase the effective chain density inthe organic polymer component contained in the finally formed curedarticle, so that it becomes easier to obtain a rubber-like cured articlehaving a high strength and a high elongation property.

The above described polyoxyalkylene polymer is essentially a polymerhaving the repeating units represented by the general formula (13):—R⁹—O—  (13)where R⁹ is a divalent organic group which has 1 to 14 carbon atoms andis a straight chain or branched alkylene group. In the general formula(13), R⁹ is preferably a straight chain or branched alkylene grouphaving 1 to 14 carbon atoms, and more preferably 2 to 4 carbon atoms.Examples of the repeating units represented by the general formula (13)include:

The main chain skeleton of the polyoxyalkylene polymer may be formed ofeither only one type of repeating units or two or more types ofrepeating units. In particular, in the case where the polymer is usedfor a sealant and the like, it is preferable that the main chainskeleton is formed of a polymer containing as the main component apropylene oxide polymer because a polymer having such a main chainskeleton is amorphous and relatively low in viscosity.

Examples of the synthesis method of the polyoxyalkylene polymer includea polymerization method based on an alkaline catalyst such as KOH; apolymerization method based on a transition metal compound-porphyrincomplex catalyst prepared by reacting an organoaluminum compound withporphyrin, disclosed in Japanese Patent Laid-Open No. 61-215623;polymerization methods based on double metal cyanide complex catalysts,disclosed in Japanese Patent Publication Nos. 46-27250 and 59-15336, andU.S. Pat. Nos. 3,278,457, 3,278,458, 3,278,459, 3,427,256, 3,427,334,3,427,335 and the like; a polymerization method using a catalystcomposed of a polyphosphazene salt disclosed in Japanese PatentLaid-Open No. 10-273512, and a polymerization method using a catalystcomposed of a phosphazene compound disclosed in Japanese PatentLaid-Open No. 11-060722. However, the method concerned is not limited tothese methods.

Examples of the manufacturing method of the reactive silicongroup-containing polyoxyalkylene polymer include the methods disclosedin Japanese Patent Publication Nos. 45-36319 and 46-12154, JapanesePatent Laid-Open Nos. 50-156599, 54-6096, 55-13767, 55-13468, 57-164123,Japanese Patent Publication No. 3-2450, and U.S. Pat. Nos. 3,632,557,4,345,053, 4,366,307 and 4,960,844; and the methods manufacturingpolyoxyalkylene polymers each having a high molecular weight and anarrow molecular weight distribution such that the number averagemolecular weight is 6,000 or more and the Mw/Mn value is 1.6 or less,disclosed in Japanese Patent Laid-Open Nos. 61-197631, 61-215622,61-215623, 61-218632, 3-72527, 3-47825 and 8-231707. However, the methodconcerned is not limited to these methods.

The above described reactive silicon group-containing polyoxyalkylenepolymers may be used either each alone or in combinations of two or morethereof.

The above described saturated hydrocarbon polymers are the polymerswhich substantially do not contain carbon-carbon unsaturated bonds otherthan aromatic rings; the polymers forming the skeletons of the saturatedhydrocarbon polymers can be obtained by the methods in which (1) olefincompounds having 1 to 6 carbon atoms such as ethylene, propylene,1-butene and isobutylene are polymerized as main monomers, and (2) dienecompounds such as butadiene and isoprene are homopolymerized orcopolymerized with the above described olefin compounds and thenhydrogenation is applied; however, isobutylene polymers and hydrogenatedpolybutadiene polymers are preferable because functional groups can beeasily introduced into the terminals of these polymers, the molecularweights of these polymers can be easily controlled and the number of theterminal functional groups can be increased; and isobutylene polymersare particularly preferable because of the ease of the synthesisthereof.

The polymers having saturated hydrocarbon polymers as the main chainskeleton are characterized in that the polymers each having such askeleton are excellent in heat resistance, weather resistance,durability and moisture blocking property.

The isobutylene polymers may be formed in such a way that all themonomer units are solely isobutylene units, or may be copolymers withmonomers other than isobutylene units; however, from the viewpoint ofthe rubber property, in each of the polymers concerned, the content ofthe units derived from isobutylene is preferably 50 wt % or more, morepreferably 80 wt % or more, and most preferably 90 to 99 wt %.

As for the synthesis methods of saturated hydrocarbon polymers, varioustypes of polymerization methods have hitherto been reported,particularly among which are many so-called living polymerizationmethods developed in these years. It has been known that the saturatedhydrocarbon polymers, in particular, the isobutylene polymers can beeasily produced by use of the inifer polymerization discovered byKennedy et al. (J. P. Kennedy et al., J. Polymer Sci., Polymer Chem.Ed., Vol. 15, p. 2843 (1997)) in such a way that polymers having themolecular weights of the order of 500 to 100,000 can be polymerized withthe molecular weight distribution of 1.5 or less and various types offunctional groups can be introduced into the molecular terminals.

The manufacturing methods of the reactive silicon group-containingsaturated hydrocarbon polymers are described, for example, in JapanesePatent Publication Nos. 4-69659 and 7-108928, Japanese Patent Laid-OpenNos. 63-254149, 64-22904 and 1-197509, Japanese Patent Nos. 2539445 and2873395, Japanese Patent Laid-Open No. 7-53882 and the like; however,the methods concerned are not particularly limited to these methods.

Among the above described reactive silicon group-containing saturatedhydrocarbon polymers, a particular saturated hydrocarbon polymer whichhas one or more groups represented by the general formula (2) can beused as the (A5) component:—Si(OR¹)₃  (2)where R¹s are the same as described above. The (A5) component is apolymer which has such features based on the saturated hydrocarbonpolymer forming the main chain skeleton that the heat resistance,weather resistance and moisture blocking property thereof are excellent,undergoes no generation of methanol caused by the hydrolysis reaction ofthe reactive silicon groups, and is satisfactory in the recoveryproperties, durability and creep resistance of the cured article.

The above described reactive silicon group-containing saturatedhydrocarbon polymers may be used either each alone or in combinations oftwo or more thereof.

In the present invention, a particular organic polymer, belonging to the(A) component organic polymer, in which the molecular chain thereof is a(meth)acrylate copolymer can be used as the (A4) component.

No particular constraint is imposed on the (meth)acrylate monomersconstituting the main chains of the above described (meth)acrylatepolymers, but various types can be used. Examples of the monomersconcerned include (meth)acrylic acid monomers such as (meth)acrylicacid, methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl(meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate,isobutyl (meth)acrylate, tert-butyl (meth)acrylate, n-pentyl(meth)acrylate, n-hexyl (meth)acrylate, cyclohexyl (meth)acrylate,n-heptyl (meth)acrylate, n-octyl (meth)acrylate, 2-ethylhexyl(meth)acrylate, nonyl (meth)acrylate, decyl (meth)acrylate, dodecyl(meth)acrylate, phenyl (meth)acrylate, tolyl (meth)acrylate, benzyl(meth)acrylate, 2-methoxyethyl (meth)acrylate, 3-methoxybutyl(meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl(meth)acrylate, stearyl (meth)acrylate, glycidyl (meth)acrylate,2-aminoethyl (meth)acrylate, γ-(methacryloyloxypropyl)trimethoxysilane,ethylene oxide adduct of (meth)acrylic acid, trifluoromethylmethyl(meth)acrylate, 2-trifluoromethylethyl (meth)acrylate,2-perfluoroethylethyl (meth)acrylate,2-perfluoroethyl-2-perfluorobutylethyl (meth)acrylate, 2-perfluoroethyl(meth)acrylate, perfluoromethyl (meth)acrylate, diperfluoromethylmethyl(meth)acrylate, 2-perfluoromethyl-2-perfluoroethylmethyl (meth)acrylate,2-perfluorohexylethyl (meth)acrylate, 2-perfluorodecylethyl(meth)acrylate and 2-perfluorohexadecylethyl (meth)acrylate. For theabove described (meth)acrylate polymers, (meth)acrylate monomers can becopolymerized with the following vinyl monomers. Examples of the vinylmonomers concerned include styrene monomers such as styrene,vinyltoluene, α-methylstyrene, chlorostyrene, and styrenesulfonic acidand the salts thereof; fluorine containing vinyl monomers such asperfluoroethylene, perfluoropropylene and fluorinated vinylidene;silicon containing vinyl monomers such as vinyltrimethoxysilane andvinyltriethoxysilane; maleic anhydride, maleic acid, and monoalkylesters and dialkyl esters of maleic acid; fumaric acid, and monoalkylesters and dialkyl esters of fumaric acid; maleimide monomers such asmaleimide, methylmaleimide, ethylmaleimide, propylmaleimide,butylmaleimide, hexylmaleimide, octylmaleimide, dodecylmaleimide,stearylmaleimide, phenylmaleimide, cyclohexylmaleimide; nitrilegroup-containing vinyl monomers such as acrylonitrile andmethacrylonitrile; amide group-containing vinyl monomers such asacrylamide and methacrylamide; vinyl esters such as vinyl acetate, vinylpropionate, vinyl pivalate, vinyl benzoate and vinyl cinnamate; alkenessuch as ethylene and propylene; conjugated dienes such as butadiene andisoprene; and vinyl chloride, vinylidene chloride, allyl chloride andallylalcohol. These monomers may be used either each alone or two ormore of these monomers may be copolymerized. Among these, from theviewpoint of the physical properties of the products, polymers formed ofstyrene monomers and (meth)acrylic acid monomers are preferable. Morepreferable are the (meth)acryl polymers formed of acrylate monomers andmethacrylate monomers, and particularly preferable are the acrylpolymers formed of acrylate monomers. For general constructionapplications, the butyl acrylate monomers are further preferable becausecompositions concerned each are required to have physical propertiesincluding a low viscosity, and the cured articles each are required tohave physical properties including a low modulus, a high elongationproperty, a weather resistance and a heat resistance. On the other hand,for applications to vehicles and the like where oil resistance isrequired, copolymers made of ethyl acrylate as the main material arefurther preferable. The copolymers made of ethyl acrylate as the mainmaterial are excellent in oil resistance, but slightly tend to be poorin low-temperature property (low-temperature resistance); for thepurpose of improving the low-temperature property thereof, part of ethylacrylate can be replaced with butyl acrylate. However, with the increaseof the ratio of butyl acrylate, the satisfactory oil resistance comes tobe degraded, so that for the application to the use requiring oilresistance, the ratio of butyl acrylate is set preferably at 40% orless, and more preferably at 30% or less. Additionally, it is alsopreferable to use 2-methoxyethyl acrylate and 2-ethoxyethyl acrylatewhich have side chain alkyl groups containing oxygen atoms introducedfor the purpose of improving the low-temperature property and the likewithout degrading the oil resistance; in this connection, it is to benoted that the introduction of alkoxy groups having an ether bond in theside chains tends to degrade the heat resistance, so that the ratio ofsuch an acrylate is preferably 40% or less when heat resistance isrequired. It is possible to obtain appropriate polymers by varying theratio in consideration of the required physical properties such as oilresistance, heat resistance and low-temperature property according tothe various applications and the demanded objectives. Examples of thepolymers excellent in the balance between the physical propertiesincluding the oil resistance, heat resistance, low-temperature propertyand the like include a copolymer of ethyl acrylate/butylacrylate/2-methoxyethyl acrylate (40 to 50/20 to 30/30 to 20 in ratio byweight), this copolymer imposing no constraint on the polymersconcerned. In the present invention, these preferable monomers can becopolymerized with other monomers, and moreover, block copolymerizedwith other monomers; in such cases, it is preferable that the preferablemonomers are contained in 40% or more in ratio by weight. Incidentally,it is to be noted that in the above form of presentation, for example,“(meth)acrylic acid” means acrylic acid and/or methacrylic acid.

No particular constraint is imposed on the synthesis methods of the(meth)acrylate copolymers (A4), and the methods well known in the artcan be applied. However, polymers obtained by the usual free radicalmethods using azo compounds and peroxides as polymerization initiatorshave a problem such that the molecular weight distribution values of thepolymers are generally larger than 2 and the viscosities of the polymersare high. Accordingly, it is preferable to apply living radicalpolymerization methods for the purpose of obtaining (meth)acrylatecopolymers being narrow in molecular weight distribution and low inviscosity, and moreover, having cross-linking functional groups at themolecular chain terminals in a high ratio.

Among “the living radical polymerization methods,” “the atom transferradical polymerization method” in which (meth)acrylate monomers arepolymerized by use of an organic halogenated compound or a halogenatedsulfonyl compound as an initiator and a transition metal complex as acatalyst has, in addition to the features of the above described “livingradical polymerization methods,” halogen atoms at the terminalsrelatively favorable for the functional group conversion reaction and islarge in freedom for designing the initiator and the catalyst, so thatthe atom transfer radical polymerization method is further preferable asa method for manufacturing (meth)acrylate copolymers having particularfunctional groups. Examples of the atom transfer radical polymerizationmethod include the method reported by Matyjaszewski et al. in Journal ofthe American Chemical Society (J. Am. Chem. Soc.), Vol. 117, p. 5614(1995).

A cured article obtained by curing a curable composition which containsa reactive silicon group-containing (meth)acrylate copolymer sometimesexhibits a smaller elongation as compared to curable compositions whichcontain organic polymers having other main chain skeletons such aspolyoxyalkylene polymers. Even when there is used a (meth)acrylatecopolymer produced by use of the above described “living radicalpolymerization method” or the above described “atom transfer radicalpolymerization method,” sometimes the elongation is insufficient and thedurability is poor. The durability of such a (meth)acrylate copolymercan be markedly improved by using as the reactive silicon groups thesilicon-containing functional groups having three or more hydrolyzablegroups on the one or more silicon atoms thereof; the improvement effectof the durability is more significant in such a copolymer than inorganic polymers having other main chain skeletons.

As a manufacturing method of a reactive silicon group-containing(meth)acrylate copolymer, for example, Japanese Patent Publication Nos.3-14068 and 4-55444, and Japanese Patent Laid-Open No. 6-211922 and thelike disclose manufacturing methods which apply the free radicalpolymerization methods using chain transfer agents. Additionally,Japanese Patent Laid-Open No. 9-272714 and the like disclose amanufacturing method which applies the atom transfer radicalpolymerization method. However, the manufacturing method concerned isnot limited to these methods.

Additionally, among the above described reactive silicongroup-containing (meth)acrylate copolymers, a particular (meth)acrylatecopolymer having one or more groups represented by the general formula(2) can be used as the (A6) component:—Si(OR¹)₃  (2)where R¹s are the same as described above. The (A6) component is apolymer which has such features based on the (meth)acrylate copolymerforming the main chain skeleton that the heat resistance, weatherresistance and chemical resistance are excellent, undergoes nogeneration of methanol caused by the hydrolysis reaction of the reactivesilicon groups, and is satisfactory in the recovery properties,durability and creep resistance of the cured article.

The reactive silicon group in the above described (A6) component may belocated at the terminals of the organic polymer molecule chain or in theinner portion of the chain, or both at the terminals and in the innerportion. In particular, the reactive silicon groups located at theterminals of the polymer main chain are preferable because such groupsincrease the effective network-chain content in the polymer componentcontained in the finally formed cured article, so that it becomes easierto obtain a rubber-like cured article having a high strength and a highelongation property.

As the polymerization method to produce the above described (A6)component, the living radical polymerization method is preferablebecause this method can lead to a narrow molecular weight distributionand a low viscosity, and can allow the introduction of cross-linkingfunctional groups into the molecular chain terminals in a highproportion; the atom transfer radical polymerization method isparticularly preferable.

The above described reactive silicon group-containing (meth)acrylatecopolymers may be used each alone or in combinations of two or morethereof.

These reactive silicon group-containing organic polymers may be usedeither each alone or in combinations of two or more thereof.Specifically, there can be used organic polymers formed by blending twoor more polymers selected from the group consisting of the reactivesilicon group-containing polyoxyalkylene polymers, the reactive silicongroup-containing saturated hydrocarbon polymers, and the reactivesilicon group-containing (meth)acrylate copolymers.

The manufacturing methods of the organic polymers formed by blending thereactive silicon group-containing polyoxyalkylene polymers with thereactive silicon group-containing (meth)acrylate copolymers are proposedin Japanese Patent Laid-Open Nos. 59-122541, 63-112642, 6-172631,11-116763 and the like. However, the manufacturing method concerned isnot limited to these methods.

It is known that the organic polymer formed by blending a reactivesilicon group-containing polyoxyalkylene polymer with a reactive silicongroup-containing (meth)acrylate copolymer is poor in recovery propertiesas compared to the case where a polyoxyalkylene polymer is used alone.Accordingly, as the polyoxyalkylene polymer component in the abovedescribed blended organic polymer, the polyoxyalkylene polymer (A3)having one or more groups represented by the general formula (2) isused:—Si(OR¹)₃  (2)where R¹s are the same as described above; the organic polymer formed byblending the (A3) polymer with the reactive silicon-group containing(meth)acrylate copolymer (A4) exhibits excellent weather resistance andadhesion based on the (A4) component, and simultaneously has excellentrecovery properties, durability and creep resistance based on the (A3)component.

A preferable specific example of the (A4) component (meth)acrylatecopolymer is based on a production method in which a reactive silicongroup-containing polyoxyalkylene polymer is blended with a copolymerhaving a molecular chain substantially formed of the following two(meth)acrylate monomer units: one (meth)acrylate monomer unit has thealkyl groups having 1 to 8 carbon atoms represented by the followinggeneral formula (14):

where R¹⁰ represents a hydrogen atom or a methyl group, and R¹¹represents an alkyl group having 1 to 8 carbon atoms; and the other(meth)acrylate monomer unit has the alkyl groups having 10 or morecarbon atoms represented by the following general formula (15):

where R¹⁰ is the same as described above, and R¹² represents an alkylgroup having 10 or more carbon atoms.

In the general formula (14), examples of R¹¹ include alkyl groups having1 to 8 carbon atoms, preferably 1 to 4 carbon atoms and furtherpreferably 1 to 2 carbon atoms such as a methyl group, an ethyl group, apropyl group, a n-butyl group, a tert-butyl group and a 2-ethylhexylgroup. It is also to be noted that R¹¹ may represent either one type oradmixtures of two or more types.

In the above general formula (15) , examples of R¹² include long chainalkyl groups having 10 or more carbon atoms, usually 10 to 30 carbonatoms, and preferably 10 to 20 carbon atoms such as a lauryl group, atridecyl group, a cetyl group, a stearyl group and a behenyl group. Itis also to be noted that R¹² may represent, similarly to R¹¹, either onetype or admixtures of two or more types.

The molecular chain of the above described (meth)acrylate copolymer issubstantially formed of the monomer units represented by formulas (14)and (15): “substantially” as referred to here means that in thecopolymer concerned the sum content of the monomer unit of formula (14)and the monomer unit of formula (15) exceeds 50 wt %. The sum content ofthe monomer units of formulas (14) and (15) is preferably 70 wt % ormore.

Additionally, the abundance ratio by weight of the monomer unit offormula (14) to the monomer unit of formula (15) is preferably 95:5 to40:60, and further preferably 90:10 to 60:40.

Examples of the monomer units other than the monomer units of formulas(14) and (15) which may be contained in the above described copolymerinclude acrylic acids such as acrylic acid and methacrylic acid;monomers containing amide groups such as acrylamide, methacrylamide,N-methylolacrylamide and N-methylolmethacrylamide, epoxy groups such asglycidylacrylate and glycidylmethacrylate, and amino groups such asdiethylaminoethylacrylate, diethylaminoethylmethacrylate and aminoethylvinyl ether; and monomer units derived from acrylonitrile, styrene,α-methylstyrene, alkyl vinyl ethers, vinyl chloride, vinyl acetate,vinyl propionate and ethylene.

The organic polymers formed by blending a reactive silicongroup-containing saturated hydrocarbon polymer with a reactive silicongroup-containing (meth)acrylate copolymer are proposed in JapanesePatent Laid-Open Nos. 1-168764, 2000-186176 and the like. However theorganic polymer concerned is not limited to these organic polymers.

Moreover, for the production method of the organic polymers formed byblending the (meth)acrylate copolymers having the reactive siliconfunctional groups, there can be used additional methods in which(meth)acrylate monomers are polymerized in the presence of a reactivesilicon group-containing organic polymer. These methods are disclosedspecifically in Japanese Patent Laid-Open Nos. 59-78223, 59-168014,60-228516, 60-228517 and the like. However, the method concerned is notlimited to these methods.

For the (B) component in the present invention, there can be used asilicate, which has a function to improve the recovery properties,durability and creep resistance of the organic polymer that is the (A)component of the present invention.

A silicate that is the (B) component is a tetraalkoxysilane representedby the general formula (16) or the partially hydrolyzed condensatesthereof:Si(OR¹³)₄  (16)where R¹³s each are independently a hydrogen atom or a monovalenthydrocarbon group selected from an alkyl group having 1 to 20 carbonatoms, an aryl group having 6 to 20 carbon atoms, and an aralkyl grouphaving 7 to 20 carbon atoms.

Specific examples of the silicate include tetraalkoxysilanes(tetraalkylsilicates) such as tetramethoxysilane, tetraethoxysilane,ethoxytrimethoxysilane, dimethoxydiethoxysilane, methoxytriethoxysilane,tetra-n-propoxysilane, tetra-i-propoxysilane, tetra-n-butoxysilane,tetra-i-butoxysilane and tetra-tert-butoxysilane, and the partiallyhydrolyzed condensates of these silanes.

The partially hydrolyzed condensates of the tetraalkoxysilanes arepreferable because these condensates are lager in the improvement effectof the recovery properties, durability and creep resistance of thepresent invention than the tetraalkoxysilanes.

Examples of the above described partially hydrolyzed condensate of atetraalkoxysilane include a condensate obtained by the usual process. Inthe process, water is added to a tetraalkoxysilane to partiallyhydrolyze the tetraalkoxysilane, and then condensation reaction occurs.Additionally, partially hydrolyzed condensates of organosilicatecompounds are commercially available. Examples of such condensatesinclude Methyl silicate 51 and Ethyl silicate 40 (both manufactured byColcoat Co., Ltd.).

The silicate (B) in combination with the (A1) component, the (A7)component or the (A8) component of the present invention exhibitsfurther satisfactory improvement effects of the recovery properties,durability and creep resistance. In particular, the silicate (B) incombination with the (A1) component exhibits satisfactory improvementeffects of recovery properties, durability and creep resistance.

Additionally, the silicate has effects to improve the adhesion, waterresistant adhesion, moisture and heat resistant adhesion and surfaceweather resistance of the curable composition of the present invention.

The used amount of the (B) component is preferably 0.1 to 10 parts byweight, and more preferably 1 to 5 parts by weight in relation to 100parts by weight of the (A) component. When the blended amount of the (B)component is less than the above described ranges, sometimes theimprovement effects of the recovery properties, durability and creepresistance is insufficient, while when the blended amount of the (B)component exceeds the above described ranges, sometimes the curing ratebecomes slow. The above described silicates may be used each alone or asadmixtures of two or more thereof.

In the present invention, as the (C) component, a tin carboxylate can beused. The use of the tin carboxylate as a silanol condensation catalystfor the organic polymer that is the (A1) component of the presentinvention makes it possible to increase the recovery properties,durability and creep resistance of the obtained cured article ascompared to other silanol condensation catalysts.

No particular constraint is imposed on the tin carboxylates (C) used inthe present invention, and various compounds can be used.

Here, as the carboxylic acids having the acid radicals of the tincarboxylates (C), preferably used are compounds containing hydrocarbonbased carboxylic acid radicals having 2 to 40 carbon atoms inclusive ofthe carbonyl carbon atom; because of availability, hydrocarbon basedcarboxylic acids having 2 to 20 carbon atoms are particularly preferablyused.

Specific examples include straight chain saturated fatty acids such asacetic acid, propionic acid, butyric acid, valeric acid, caproic acid,enanthic acid, caprylic acid, 2-ethylhexanoic acid, pelargonic acid,capric acid, undecanoic acid, lauric acid, tridecanoic acid, myristicacid, pentadecanoic acid, palmitic acid, heptadecanoic acid, stearicacid, nonadecanoic acid, arachic acid, behenic acid, lignoceric acid,cerotic acid, montanic acid, melissic acid and lacceric acid; monoeneunsaturated fatty acids such as undecylenic acid, linderic acid, tsuzuicacid, physeteric acid, myristoleic acid, 2-hexadecenoic acid,6-hexadecenoic acid, 7-hexadecenoic acid, palmitoleic acid, petroselicacid, oleic acid, elaidic acid, asclepinic acid, vaccenic acid, gadoleicacid, gondoic acid, cetoleic acid, erucic acid, brassidic acid,selacholeic acid, ximenic acid, lumequeic acid, acrylic acid,methacrylic acid, angelic acid, crotonic acid, isocrotonic acid and10-undecenoic acid; polyene unsaturated fatty acids such as linoelaidicacid, linoleic acid, 10,12-octadecadienoic acid, hiragoic acid,α-eleostearic acid, β-eleostearic acid, punicic acid, linolenic acid,8,11,14-eicosatrienoic acid, 7,10,13-docosatrienoic acid,4,8,11,14-hexadecatetraenoic acid, moroctic acid, stearidonic acid,arachidonic acid, 8,12,16,19-docosatetraenoic acid,4,8,12,15,18-eicosapentaenoic acid, clupanodonic acid, nishinic acid anddocosahexaenoic acid; branched fatty acids such as 1-methylbutyric acid,isobutyric acid, 2-ethylbutyric acid, isovaleric acid, tuberculostearicacid, pivalic acid and neodecanoic acid; fatty acids having a triplebond such as propiolic acid, tariric acid, stearolic acid, crepenynicacid, ximenynic acid and 7-hexadecynoic acid; alicyclic carboxylic acidssuch as naphthenic acid, malvalic acid, sterculic acid, hydnocarpicacid, chaulmoogric acid and gorlic acid; oxygen containing fatty acidssuch as acetoacetic acid, ethoxy acetic acid, glyoxylic acid, glycolicacid, gluconic acid, sabinic acid, 2-hydroxytetradecanoic acid, ipurolicacid, 2-hydroxyhexadecanoic acid, jalapinolic acid, juniperic acid,ambrettolic acid, aleuritic acid, 2-hydroxyoctadecanoic acid,12-hydroxyoctadecanoic acid, 18-hydroxyoctadecanoic acid,9,10-dihydroxyoctadecanoic acid, ricinoleic acid, camlolenic acid,licanic acid, pheronic acid and cerebronic acid; and halogen substitutedmonocarboxylic acids such as chloroacetic acid, 2-chloroacrylic acid andchlorobenzoic acid. Examples of aliphatic dicarboxylic acids includesaturated dicarboxylic acids such as adipic acid, azelaic acid, pimelicacid, suberic acid, sebacic acid, ethylmalonic acid, glutaric acid,oxalic acid, malonic acid, succinic acid, oxydiacetic acid; andunsaturated dicarboxylic acids such as maleic acid, fumaric acid,acetylenedicarboxylic acid and itaconic acid. Examples of aliphaticpolycarboxylic acids include tricarboxylic acids such as aconitic acid,citric acid and isocitric acid. Examples of aromatic carboxylic acidsinclude aromatic monocarboxylic acids such as benzoic acid,9-anthracenecarboxylic acid, atrolactic acid, anisic acid,isopropylbenzoic acid, salicylic acid and toluic acid; and aromaticpolycarboxylic acids such as phthalic acid, isophthalic acid,terephthalic acid, carboxyphenylacetic acid and pyromellitic acid.Additional other examples include amino acids such as alanine, leucine,threonine, aspartic acid, glutamic acid, arginine, cysteine, methionine,phenylalanine, tryptophane and histidine.

The above described carboxylic acid is preferably 2-ethylhexanoic acid,octylic acid, neodecanoic acid, oleic acid or naphthenic acid, becauseparticularly these acids are easily available and low in price, andsatisfactorily compatible with the (A1) component.

When the melting point of the carboxylic acid is high (the crystallinityis high), the tin carboxylate having the acid radical of the carboxylicacid has similarly a high melting point and is hardly handlable (poor inworkability). Accordingly, the melting point of the carboxylic acid ispreferably 65° C. or lower, more preferably −50 to 50° C., andparticularly preferably −40 to 35° C.

Additionally, when the number of the carbon atoms in the above describedcarboxylic acid is large (the molecular weight thereof is large), thetin carboxylate having the acid radical takes a solid form or a highlyviscous liquid form, becoming hardly handlable (degrading theworkability thereof). On the contrary, when the number of the carbonatoms in the above described carboxylic acid is small (the molecularweight thereof is small), sometimes the tin carboxylate having the acidradical contains such components that are easily evaporated by heating,and the catalytic activity of the metal carboxylate is degraded.Particularly, under the conditions that the composition is extendedthinly (a thin layer), sometimes the evaporation due to heating becomessignificant, and the catalytic activity of the metal carboxylate islargely degraded. Accordingly, for the above described carboxylic acid,the number of the carbon atoms inclusive of the carbonyl carbon atom ispreferably 2 to 20, more preferably 6 to 17, and particularly preferably8 to 12.

From the viewpoint of easy handlability (workability and viscosity) ofthe tin carboxylate, the tin carboxylate is preferably a tindicarboxylate or a tin monocarboxylate, and more preferably a tinmonocarboxylate.

As the above described tin monocarboxylate, preferable is a divalent Sncompound represented by the general formula (17):Sn(OCOR)₂  (17)where Rs each are a substituted or unsubstituted hydrocarbon group, andmay include carbon-carbon double bonds, and the two RCOO— groups maybethe same or different, or a tetravalent Sn compound represented by thegeneral formula (18):Sn(OCOR)₄  (18)where Rs are the same as described above, and two RCOO— groups may bethe same or different. From the viewpoints of curability andavailability, the divalent Sn compound represented by the generalformula (17) is more preferable.

Additionally, the above described tin carboxylate (C) is preferably atin carboxylate (tin 2-ethylhexanoate and the like) in which theα-carbon atom of the carboxyl group is a tertiary carbon atom or a tincarboxylate (tin neodecanoate, tin pivalate and the like) in which theα-carbon atom of the carboxyl group is a quaternary carbon atom becauseof rapid curing rate, and is particularly preferably a tin carboxylatein which the carbon atom adjacent to the carbonyl group is a quaternarycarbon atom.

In the present invention, among the tin carboxylates (C), a particulartin carboxylate in which the α-carbon atom of the carboxyl group is aquaternary carbon atom is used as the (C1) component.

Examples of the (C1) component tin carboxylate include the tin salt of achain fatty acid represented by the general formula (19):

where R¹⁴, R¹⁵ and R¹⁶ each are independently a substituted orunsubstituted monovalent organic group, and the group may includecarboxyl groups; the tin salt of a cyclic fatty acid represented by thegeneral formula (20):

where R¹⁷ is a substituted or unsubstituted monovalent organic group,R¹⁸ is a substituted or unsubstituted divalent organic group, and thesegroups each may include carboxyl groups; or the tin salt of a cyclicfatty acid represented by the general formula (21):

where R¹⁹ is a substituted or unsubstituted trivalent organic group, andthe group may include carboxyl groups. Specific examples of thecarboxylic acid having the acid radical of the tin carboxylate (C1)include chain monocarboxylic acids such as pivalic acid,2,2-dimethylbutyric acid, 2-ethyl-2-methylbutyric acid,2,2-diethylbutyric acid, 2,2-dimethylvaleric acid,2-ethyl-2-methylvaleric acid, 2,2-diethylvaleric acid,2,2-dimethylhexanoic acid, 2,2-diethylhexanoic acid,2,2-dimethyloctanoic acid, 2-ethyl-2,5-dimethylhexanoic acid,neodecanoic acid, versatic acid, 2,2-dimethyl-3-hydroxypropionic acid;chain dicarboxylic acids such as dimethylmalonic acid,ethylmethylmalonic acid, diethylmalonic acid, 2,2-dimethylsuccinic acid,2,2-diethylsuccinic acid, 2,2-dimethylglutaric acid; chain tricarboxylicacids such as 3-methylisocitric acid and 4,4-dimethylaconitic acid; andcyclic carboxylic acids such as 1-methylcyclopentane carboxylic acid,1,2,2-trimethyl-1,3-cyclopentane dicarboxylic acid, 1-methylcyclohexanecarboxylic acid, 2-methylbicyclo[2.2.1]-5-heptene-2-carboxylic acid,2-methyl-7-oxabicyclo[2.2.1]-5-heptene-2-carboxylic acid, 1-adamantanecarboxylic acid, bicyclo[2.2.1]heptane-1-carboxylic acid andbicyclo[2.2.2]octane-1-carboxylic acid. Compounds having such structuresare abundant in natural products, and such compounds can also be used.

Particularly, the tin monocarboxylates are more preferable because thecompatibility thereof with the (A1) component and the workabilitythereof are satisfactory; moreover, the tin chain-monocarboxylates aremore preferable. Additionally, because of easy availability, tinpivalate, tin neodecanoate, tin versatate, tin 2,2-dimethyloctanoate,tin 2-ethyl-2,5-dimethylhexanoate and the like are particularlypreferable.

Similarly to the case of the above described (C) component, divalent tincarboxylates and tetravalent tin carboxylates can be cited for the (C1)component; however, divalent tin carboxylates are more preferable fromthe viewpoints of the curability and availability.

The number of the carbon atoms in a carboxylic acid having the acidradical of the (C1) component is preferably 5 to 20, more preferably 6to 17, and particularly preferably 8 to 12. When the number of thecarbon atoms exceeds these ranges, sometimes unpreferably such a tincarboxylate tends to take a solid form, the compatibility thereof withthe (A1) component is degraded, and the catalytic activity tends to bedegraded. On the other hand, when the number of the carbon atoms issmall, unpreferably the volatility and the odor tend to be increased,and the thin-layer curability of the curable composition is degraded.

From these viewpoints, as the (C1) component, particularly preferableare tin(II) neodecanoate, tin(II) versatate, tin(II)2,2-dimethyloctanoate, tin(II) 2-ethyl-2,5-dimethylhexanoate, tin(IV)neodecanoate, tin(IV) versatate, tin(IV) 2,2-dimethyloctanoate and tin(IV) 2-ethyl-2,5-dimethylhexanoate.

The used amount of each of the (C) component and the (C1) component ispreferably of the order of 0.01 to 20 parts by weight, and furtherpreferably of the order of 0.5 to 10 parts by weight, in relation to 100parts by weight of the (A1) component. When the blended amount concernedis smaller than the above described ranges, sometimes unpreferably thecuring rate becomes slow, and the curing reaction hardly proceeds to asufficient extent. On the other hand, when the blended amount concernedexceeds the above described ranges, sometimes unpreferably the work lifebecomes too short and the workability is degraded, and this is notpreferable from the viewpoint of the storage stability.

Additionally, the (C) component and the (C1) component may be used eachalone or in combinations of two or more thereof.

When the activity is low only with the (C) component and the (C1)component, and accordingly an appropriate curability cannot be obtained,an amine compound may be added as an auxiliary catalyst.

Various such amines are described, for example, in Japanese PatentLaid-Open No. 5-287187; specific examples of the amine compound includealiphatic primary amines such as methylamine, ethylamine, propylamine,isopropylamine, butylamine, amylamine, hexylamine, octylamine,2-ethylhexylamine, nonylamine, decylamine, laurylamine, pentadecylamine,cetylamine, stearylamine and cyclohexylamine; aliphatic secondary aminessuch as dimethylamine, diethylamine, dipropylamine, diisopropylamine,dibutylamine, diamylamine, dioctylamine, di(2-ethylhexyl)amine,didecylamine, dilaurylamine, dicetylamine, distearylamine,methylstearylamine, ethylstearylamine and butylstearylamine; aliphatictertiary amines such as triethylamine, triamylamine, trihexylamine andtrioctylamine; aliphatic unsaturated amines such as triallylamine andoleylamine; aromatic amines such as laurylaniline, stearylaniline,triphenylamine, N,N-dimethylaniline and dimethylbenzylaniline; and otheramines such as monoethanolamine, diethanolamine, triethanolamine,dimethylaminoethanol, diethylenetriamine, triethylenetetramine,tetraethylenepentamine, benzylamine, diethylaminopropylamine,xylylenediamine, ethylenediamine, hexamethylenediamine,dodecamethylenediamine, dimethylethylenediamine, triethylenediamine,guanidine, diphenylguanidine, N,N,N′,N′-tetramethyl-1,3-butanediamine,N,N,N′,N′-tetramethylethylenediamine,2,4,6-tris(dimethylaminomethyl)phenol, morpholine, N-methylmorpholine,2-ethyl-4-methylimidazole, and 1,8-diazabicyclo (5,4,0)undecene-7 (DBU).However, the amine is not limited to these examples.

The blended amount of the above described amine compound is preferablyof the order of 0.01 to 20 parts by weight, and more preferably 0.1 to 5parts by weight in relation to 100 parts by weight of the (A1)component. When the blended amount of the amine compound is less than0.01 part by weight, sometimes the curing rate becomes slow, and thecuring reaction hardly proceeds to a sufficient extent. On the otherhand, when the blended amount of the amine compound exceeds 20 parts byweight, sometimes the pot life tends to become too short, and this isnot preferable from the viewpoint of workability.

In the present invention, an organotin catalyst can be used as the (D)component. When such an organotin catalyst is used as a silanolcondensation catalyst for a reactive silicon group-containing organicpolymer, the organotin catalyst is higher in catalytic activity, ascompared to other silanol condensation catalysts, to yield a curablecomposition satisfactory in deep-part curability and adhesion. However,the organotin catalyst, according to the addition amount thereof,degrades the recovery properties, durability and creep resistance of thecured article derived from the obtained curable composition.

By use of the organic polymer that is the (A1) component of the presentinvention, as the polymer component, the curable composition added withthe (D) component organotin catalyst is made to be high in catalyticactivity, satisfactory in deep-part curability and adhesion, and therecovery properties, durability and creep resistance of the obtainedcured article can be maintained at high levels.

On the other hand, when an adhesive or a sealant which contains as themain component a reactive silicon group-containing organic polymer isused in applications requiring durability, the above described (C)component tin carboxylate is often used as a curing catalyst. However,when the tin carboxylate is used as a curing catalyst, the sealantremaining, if any, as a thin layer portion around joints sometimesresults in a hardly curable thin layer portion, particularly, a portionremaining uncured under high temperature and high humidity conditions.On the other hand, the above described organotin catalyst (D) is used asa curing catalyst, the recovery properties and durability are degradedas described above, whereas the curability of the thin layer portion issatisfactory. Accordingly, when the (A1) component organic polymer ofthe present invention and the (D) component organotin catalyst are usedin combination, the curability of the thin layer portion can be markedlyimproved while the recovery properties and durability of the obtainedcured article are being maintained at high levels.

However, even when the (A1) component organic polymer of the presentinvention is combined with the (D) component organotin catalyst,sometimes the recovery properties and durability are slightly degradeddepending on the addition amount of the (D) component organotincatalyst. Accordingly, it is more preferable that the (D) componentorganotin catalyst and the (C) component tin carboxylate aresimultaneously used as the curing catalyst, and the addition amount ofthe (D) component is decreased to such an extent that sufficientcurability, deep-part curability, adhesion and thin-layer curability canbe obtained.

Specific examples of the above described organotin catalyst (D) includedialkyltin carboxylates, dialkyltin oxides, and the compoundsrepresented by the general formula (22):Q_(g)Sn(OZ)_(4-g) or [Q₂Sn(OZ)]₂O  (22)where Q represents a monovalent hydrocarbon group having 1 to 20 carbonatoms, Z represents a monovalent hydrocarbon group having 1 to 20 carbonatoms or an organic group having therein one or more functional groupscapable of forming coordination bonds with Sn, and g is any one of 0, 1,2, and 3. The reaction products between tetravalent tin compounds suchas dialkyltin oxides and dialkyltin diacetates and low-molecular-weight,hydrolyzable silicon group-containing silicon compounds such astetraethoxysilane, methyltriethoxysilane, diphenyldimethoxysilane andphenyltrimethoxysilane can also be used as the (D) component. Amongthese compounds, the compounds represented by the general formula (22),namely, chelate compounds such as dibutyltin bis(acetylacetonate) andtin alcoholates are preferable because of high activity as silanolcondensation catalyst.

Specific examples of the dialkyltin carboxylates include dibutyltindilaurate, dibutyltin diacetate, dibutyltin diethylhexanolate,dibutyltin dioctanoate, dibutyltin dimethylmaleate, dibutyltindiethylmaleate, dibutyltin dibutylmaleate, dibutyltin diisooctylmaleate,bibutyltin ditridecylmaleate, dibutyltin dibenzylmaleate, dibutyltinmaleate, dioctyltin diacetate, dioctyltin distearate, dioctyltindilaurate, dioctyltin diethylmaleate, and dioctyltin diisooctylmaleate.

Specific examples of the dialkyltin oxides include dibutyltin oxide,dioctyltin oxide, and a mixture composed of dibutyltin oxide and aphthalate.

Specific examples of the chelate compounds include the following:

However, the chelate compounds concerned are not limited to theseexamples. Among these chelate compounds, dibutyltin bis(acetylacetonate)is most preferable because it is high in catalytic activity, low incost, and easily available.

Specific examples of the tin alcoholates include the following:

However, the tin alcoholates concerned are not limited to theseexamples. Among these tin alcoholates, dialkylltin dialkoxides arepreferable. In particular, dibutyltin dimethoxide is preferable becauseit is low in cost and easily available.

The used amount of the (D) component is preferably of the order of 0.01to 20 parts by weight, and furthermore preferably of the order of 0.1 to10 parts by weight in relation to 100 parts by weight of the (A1)component. When the blended amount concerned is smaller than the abovedescribed ranges, sometimes unpreferably the curing rate becomes slow,and the curing reaction hardly proceeds to a sufficient extent. On theother hand, when the blended amount concerned exceeds the abovedescribed ranges, sometimes unpreferably the work life becomes too shortand the workability is degraded, and this is not preferable from theviewpoint of the storage stability.

The used amounts of the (C) and (D) components, when used in combinationas the curing catalyst, are preferably 0.5 to 20 parts by weight and0.01 to 10 parts by weight, respectively, and more preferably, 1 to 10parts by weight and 0.02 to 5 parts by weight, respectively, in relationto 100 parts by weight of the (A1) component. When the blended amount ofthe (C) component is less than the above described ranges, sometimes thecuring rate becomes slow, while when the blended amount concernedexceeds the above described ranges, sometimes the work life becomes tooshort and the workability is degraded. When the blended amount of the(D) component is smaller than the above described ranges, sometimes theimprovement effects of the curability, deep-part curability, adhesionand thin-layer curability become insufficient, while when the blendedamount concerned exceeds the above described ranges, sometimes therecovery properties, durability and creep resistance of the obtainedcured article are degraded.

Additionally, the (D) component may be used each alone or incombinations of two or more thereof.

In the present invention, a non-tin catalyst can be used as component(E). Such a non-tin catalyst has the function of increasing the recoveryproperties, durability and creep resistance of the obtained curedarticle when used as a silanol condensation catalyst for an organicpolymer (component (A1)) of the present invention, as compared withother silanol condensation catalysts. The component (E) non-tin catalystis also an environmentally friendly curing catalyst for which there is astrong desire from society.

Although the non-tin catalyst component (E) used in the presentinvention is not particularly limited, examples include carboxylic acid,a carboxylic acid metal salt other than tin carboxylate, an organicsulfonic acid, an acidic phosphate ester and an organometallic compoundcontaining a Group 3B or Group 4A metal. Examples of an organometalliccompound containing a Group 3B or Group 4A metal include organotitanatecompounds, organoaluminum compounds, organozirconium compounds andorganoboron compounds. Among these, carboxylic acid, a carboxylic acidmetal salt other than tin carboxylate and an organotitanate compound arepreferable in terms of their availability, curability and the recoveryproperties of the obtained cured article. More preferable are carboxylicacid and an organotitanate compound, and particularly preferable iscarboxylic acid.

Examples of the carboxylic acid include the above-described variouscarboxylic acids having the acid group of the component (C) tincarboxylate.

The above-described carboxylic acid, in the same manner as the tincarboxylate (C), preferably contains from 2 to 20 carbon atoms includingthe carboxylic acid carbon atom. More preferable is from 6 to 17 carbonatoms, and from 8 to 12 is particularly preferable. From the standpointof ease of handling of the carboxylic acid (workability and viscosity),a dicarboxylic acid or a monocarboxylic acid is preferable, and morepreferable is a monocarboxylic acid. The above-described carboxylic acidis more preferably a carboxylic acid wherein the α-site carbon atom ofthe carboxyl group is a tertiary carbon (2-ethylhexanoic acid, etc.) ora quaternary carbon (neodecanoic acid, pivalic acid, etc.) because ofits rapid curing rate. Particularly preferable is a carboxylic acidwherein a carbon atom adjacent to the carbonyl group is quaternary.

In view of availability, curability and workability, particularlypreferable as the carboxylic acid are 2-ethylhexanoic acid, neodecanoicacid, versatic acid, 2,3-dimethyloctanoic acid and2-ethyl-2,5-dimethylhexanoic acid.

As the carboxylic acid metal salt other than the above-described tincarboxylate, the above-described various kinds of carboxylic acid metalsalt may be suitably employed.

Of the carboxylic acid metal salts other than the above-described tincarboxylate, bismuth carboxylate, calcium carboxylate, vanadiumcarboxylate, iron carboxylate, titanium carboxylate, potassiumcarboxylate, barium carboxylate, manganese carboxylate, nickelcarboxylate, cobalt carboxylate, zirconium carboxylate and ceriumcarboxylate exhibit high catalytic activity, and are thus preferable.More preferable are bismuth carboxylate, calcium carboxylate, vanadiumcarboxylate, iron carboxylate, titanium carboxylate, potassiumcarboxylate, barium carboxylate, manganese carboxylate, and zirconiumcarboxylate, still more preferable are bismuth carboxylate, calciumcarboxylate, vanadium carboxylate, iron carboxylate, titaniumcarboxylate, and zirconium carboxylate, while most preferable amongthese are bismuth carboxylate, iron carboxylate and titaniumcarboxylate.

Further, more preferable are bismuth carboxylate, calcium carboxylate,vanadium carboxylate, titanium carboxylate, potassium carboxylate,barium carboxylate, manganese carboxylate, nickel carboxylate, cobaltcarboxylate and zirconium carboxylate in view of the fact that theobtained curable composition has low coloration and that the obtainedcured article possesses high thermal resistance and weatherability, andstill more preferable are bismuth carboxylate, calcium carboxylate,titanium carboxylate, potassium carboxylate, barium carboxylate andzirconium carboxylate.

From the standpoint of ease of handling of the carboxylic acid metalsalt (workability and viscosity), a metal salt of a monocarboxylic acidis more preferable.

Preferable carboxylic acid metal salts for such a monocarboxylic acidmetal salt are represented by the general formulae (23) to (35):Bi(OCOR)₃  (23)Ca(OCOR)₂  (24)V(OCOR)₃  (25)Fe(OCOR)₂  (26)Fe(OCOR)₃  (27)Ti(OCOR)₄  (28)K(OCOR)  (29)Ba(OCOR)₂  (30)Mn(OCOR)₂  (31)Ni(OCOR)₂  (32)Co(OCOR)₂  (33)Zr(O)(OCOR)₂  (34)Ce(OCOR)₃  (35)wherein R represents a substituted or non-substituted hydrocarbon groupand may contain a carbon-carbon double bond; and 2 RCOO— groups may bethe same or different.

Examples of the carboxylic acid group of the carboxylic acid metal saltother than the above-described tin carboxylates include the acid groupsof the various tin carboxylates exemplified as the above-describedcomponent (C).

In view of the availability and compatibility of the raw materials,specific examples of a preferable carboxylic acid metal salt includebismuth 2-ethylhexanoate (trivalent), iron 2-ethylhexanoate (divalent),iron 2-ethylhexanoate (trivalent), titanium 2-ethylhexanoate(tetravalent), vanadium 2-ethylhexanoate (trivalent), calcium2-ethylhexanoate (divalent), potassium 2-ethylhexanoate (monovalent),barium 2-ethylhexanoate (divalent) manganese 2-ethylhexanoate(divalent), nickel 2-ethylhexanoate (divalent), cobalt 2-ethylhexanoate(divalent), zirconium 2-ethylhexanoate (tetravalent), cerium2-ethylhexanoate (trivalent), bismuth neodecanoate (trivalent), ironneodecanoate (divalent), iron neodecanoate (trivalent), titaniumneodecanoate (tetravalent), vanadium neodecanoate (trivalent), calciumneodecanoate (divalent), potassium neodecanoate (monovalent), bariumneodecanoate (divalent), zirconium neodecanoate (tetravalent), ceriumneodecanoate (trivalent), bismuth oleate (trivalent), iron oleate(divalent), iron oleate (trivalent), titaniumoleate (tetravalent),vanadium oleate (trivalent), calcium oleate (divalent), potassium oleate(monovalent), barium oleate (divalent), manganese oleate (divalent),nickel oleate (divalent) cobalt oleate (divalent), zirconium oleate(tetravalent), cerium oleate (trivalent), bismuth naphthenate(trivalent), iron naphthenate (divalent), iron naphthenate (trivalent),titanium naphthenate (tetravalent), vanadium naphthenate (trivalent),calcium naphthenate (divalent), potassium naphthenate (monovalent)barium naphthenate (divalent), manganese naphthenate (divalent) nickelnaphthenate (divalent), cobalt naphthenate (divalent), zirconiumnaphthenate (tetravalent) and cerium naphthenate (trivalent).

In view of catalytic activity, more preferable are bismuth2-ethylhexanoate (trivalent), iron 2-ethylhexanoate (divalent), iron2-ethylhexanoate (trivalent), titanium 2-ethylhexanoate (tetravalent),bismuth neodecanoate (trivalent), iron neodecanoate (divalent), ironneodecanoate (trivalent), titanium neodecanoate (tetravalent), bismutholeate (trivalent), iron oleate (divalent), iron oleate (trivalent),titanium oleate (tetravalent), bismuth naphthenate (trivalent), ironnaphthenate (divalent), iron naphthenate (trivalent) and titaniumnaphthenate (tetravalent), and particularly preferable are iron2-ethylhexanoate (trivalent), iron neodecanoate (trivalent) and ironnaphthenate (trivalent).

In view of coloration, more preferred are bismuth 2-ethylhexanoate(trivalent), titanium 2-ethylhexanoate (tetravalent), calcium2-ethylhexanoate (divalent), potassium 2-ethylhexanoate (monovalent),barium 2-ethylhexanoate (divalent), zirconium 2-ethylhexanoate(tetravalent), bismuth neodecanoate (trivalent), titanium neodecanoate(tetravalent), calcium neodecanoate (divalent), potassium neodecanoate(monovalent), barium neodecanoate (divalent), zirconium neodecanoate(tetravalent), bismuth oleate (trivalent), titanium oleate(tetravalent), calcium oleate (divalent), potassium oleate (monovalent),barium oleate (divalent), zirconium oleate (tetravalent), bismuthnaphthenate (trivalent), titanium naphthenate (tetravalent), calciumnaphthenate (divalent), potassium naphthenate (monovalent), bariumnaphthenate (divalent) and zirconium naphthenate (tetravalent).

Examples of the organic sulfonic acid include toluenesulfonic acid andstyrenesulfonic acid, among others.

The acidic phosphate ester is a phosphoric acid ester containing an—O—P(═O)OH moiety and includes the below-mentioned acidic phosphateesters. Organic acidic phosphate ester compounds are preferred in viewof their compatibility and cure-catalyzing activity.

The organic acidic phosphate ester compound is represented by theformula (R²⁰—O)_(h)—P(═O)(—OH)_(3-h) (wherein h is equal to 1 or 2; andR²⁰ represents an organic residue).

Specific examples include (CH₃O)₂—P(═O)(—OH), (CH₃O)—P(═O)(—OH)₂,(C₂H₅O)₂—P(═O)(—OH), (C₂H₅O)—P(═O)(—OH)₂, (C₃H₇O)₂—P(═O)(—OH),(C₃H₇O)—P(═O)(—OH)₂, (C₄H₉O)₂—P(═O)(—OH), (C₄H₉O)—P(═O)(—OH)₂,(C₈H₁₇O)₂—P(═O)(—OH), (C₈H₁₇O)—P(═O)(—OH)₂, (C₁₀H₂₁O)₂—P(═O)(—OH),(C₁₀H₂₁O)—P(═O)(—OH)₂, (C₁₃H₂₇O)₂—P(═O)(—OH), (C₁₃H₂₇O)—P(═O)(—OH)₂,(C₁₆H₃₃O)₂—P(═O)(—OH), (C₁₆H₃₃O)—P(═O)(—OH)₂, (HO—C₆H₁₂O)₂—P(═O)(—OH),(HO—C₆H₁₂O)—P(═O)(—OH)₂, (HO—C₈H₁₆O)₂—P(═O)(—OH),(HO—C₈H₁₆O)—P(═O)(—OH)₂, {(CH₂OH)(CHOH)O}₂—P(═O)(—OH),{(CH₂OH)(CHOH)O}—P(═O)(—OH)₂, {(CH₂O)(CHOH)C₂H₄O}₂—P(═O)(—OH),{(CH₂OH)(CHOH)C₂H₄O}—P(═O)(—OH)₂ and the like, although the presentinvention is not limited to these exemplified substances.

In cases where the carboxylic acid, carboxylic acid metal salt otherthan tin carboxylate, organic sulfonic acid, and acidic phosphate esteralone results in low activity, whereby suitable curability cannot beachieved, an amine compound may be added as a promoter.

Examples of the various amine compounds that can be used include thevarious amine compounds described above as a promoter for the tincarboxylate (C).

The amount of the amine compound is preferably from about 0.01 to 20parts by weight, and more preferably from about 0.1 to 5 parts byweight, in relation to 100 parts by weight of the component (A1) organicpolymer. When the amount of the amine compound is less than 0.01 partsby weight, the curing rate may decrease, and in some cases it becomesmore difficult for the curing reaction to proceed sufficiently. On theother hand, when the amount of the amine compound is more than 20 partsby weight, pot life may become too short, which is not preferable from aworkability standpoint.

Examples of the non-tin metal compound include an organometalliccompound containing a Group 3B or Group 4A metal, as well as theabove-described carboxylic acid metal salt other than tin carboxylate.While organotitanate compounds, organoaluminum compounds,organozirconium compounds, organoboron compounds and the like arepreferable in view of their activity, the non-tin metal compound is notlimited to these examples.

Examples of the above-described organotitanate compound include titaniumalkoxides such as tetraisopropyl titanate, tetrabutyl titanate,tetramethyl titanate, tetra(2-ethylhexyl titanate), triethanolaminetitanate, and chelate compounds such as titanium chelate compounds, forexample titanium tetraacetylacetonate, titanium ethylacetoacetate,octylene glycol titanate ester, titanium lactate and the like.

Examples of the above-described organoaluminum compound include aluminumalkoxides such as aluminum isopropylate, mono-sec-butoxyaluminumdiisopropylate, and aluminum sec-butylate, and aluminum chelatecompounds, such as aluminum tris(acetylacetonate), aluminum tris(ethylacetoacetate), diisopropoxyaluminum ethylacetoacetate and the like.

Examples of the above-described organozirconium compound includezirconium alkoxides such as zirconium tetraisopropylate, zirconiumtetra-n-propylate and zirconium n-butylate, and zirconium chelatecompounds, such as zirconium tetraacetylacetonate, zirconiummonoacetylacetonate, zirconium bisacetylacetonate, zirconiumacetylacetonato-bis-etylacetoacetate, zirconium acetate and the like.

While these organotitanate compounds, organoaluminum compounds,organozirconium compounds, organoboron compounds, etc. may be each usedin combination, the use of these compounds in combination with theabove-described amine compound or acidic phosphate ester compound ispreferable from the standpoint that savings in catalyst material may berealized because activity can be increased. The use of such combinationis further preferable from the point of improved curability at elevatedtemperature and adjustment of the work life at room temperature.

The content of component (E) is preferably from 0.01 to 20 parts byweight relative in relation to 100 parts by weight of component (A1),and more preferable is from 0.5 to 10 parts by weight. An amount lessthan this range is not preferable, since the curing rate may decrease,and in some cases it becomes more difficult for the curing reaction toproceed sufficiently. On the other hand, an amount above this range isnot preferable, since work life may become too short causing adeterioration in workability, and is also not preferable in terms ofstorage stability.

Component (E) can not only be used alone, but also used in combinationwith two types or more.

In the present invention microballoons can be used as component (F). Itis known, as disclosed in Japanese Patent Publication Nos. 11-35923 and11-310772, that when such microballoons are used, workability(thread-pulling properties, thixotropy properties) of the compounddramatically improves, and the compound can become lighter and lower incost. However, it is known that depending on the added amount ofmicroballoons, the recovery properties and durability of the obtainedcurable composition cured article can deteriorate.

Using the component (A1) organic polymer of the present invention forthe polymer component allows a curable composition to which component(F) microballoons have been added to maintain high recovery propertiesand durability of the obtained cured article while dramaticallyimproving workability (thread-pulling properties).

The component (F) microballoons of the present invention (hereinafterreferred to as “balloons”), as described by CMC Books in “CurrentTechnology of Functional Fillers”, are hollow bodies constituted from aninorganic or organic material having a diameter of not more than 1 mm,and preferably not more than 500 μm. Component (F) is not particularlyrestricted, and various kinds of commonly known balloons may be used.

The average particle density of the balloons is preferably from 0.01 to1.0 g/cm³, from 0.03 to 0.7 g/cm³ is more preferable and from 0.1 to 0.5g/cm³ is particularly preferable. If the average particle density islower than this range the tensile strength of the cured article candeteriorate, while if the average particle density is greater than thisrange the workability improvement effects are sometimes insufficient.

From the standpoint of recovery properties and durability, inorganicballoons are preferable to organic balloons.

Examples of the above-described inorganic balloons include silicic acidballoons and non-silicic acid balloons. Examples of silicic-acidballoons include shirasu balloons, pearlite, glass balloons, silicaballoons and fly-ash balloons. Examples of non-silicic acid balloonsinclude alumina balloons, zirconia balloons and carbon balloons.Specific commercially-available examples of these inorganic balloonsinclude Winlite (product of Idichi Chemical) and Sankilite (product ofSanki Engineering Co., Ltd.) as shirasu balloons, Calloon (product ofNippon Sheet Glass Co.), Selstar Z-28 (product of Sumitomo 3M), MICROBALLOON (product of Emerson & Cuming Co.), CELAMIC GLASSMODULES (productof Pittsburge Corning) and GLASS BUBBLES (product of 3M) and FujiBalloon (product of Fuji Silysia Chemical Ltd.) as glass balloons, Q-CEL(product of Asahi Glass CO.) and Sylisia (product of Fuji SilysiaChemical Ltd.) as silica balloons, CEROSPHERES (product of Pfamarketing)and FILLITE (product of Fillite U.S.A.) as fly-ash balloons, BW (productof Showa Denko Co.) as alumina balloons, HOLLOW ZIRCONIUM SPHERES(product of Zircoa) as zirconia balloons, and Kurekasphere (product ofKureha Chemical Industry Co.) and Carbosphere (product of GeneralTechnologies) as carbon balloons.

Examples of the above-described organic balloons include thermosettingresin balloons and thermoplastic resin balloons. Thermosetting balloonsspecifically include phenol balloons, epoxy balloons and urea balloons,and thermoplastic balloons specifically include saran balloons,polystyrene balloons, polymethacrylate balloons, poly(vinyl alcohol)balloons and styrene-acrylic balloons. Crosslinked thermoplastic resinballoons can also be used. The term “balloons” as used here may befoamed balloons or balloons comprising a foaming agent and being foamedafter compounding to thereby render the same as a balloon.

Specific commercially-available examples of the above-described organicballoons include UCAR and PHENOLIC MICROBALLOONS (both being products ofUnion Carbide) as phenol balloons, ECCOSPHERES (product of Emerson &Cuming Co.) as epoxy balloons, ECCOSPHERES VF-O (product of Emerson &Cuming Co.) as urea balloons, SARAN MICROSPHERES (product of DowChemicals, Inc.), Expancel (product of Nihon Filament) and MatsumotoMicrosphere (product of Matsumoto Yushi-Seiyaku Co.) as saran balloons,DYLITE EXPANDABLE POLYSTYRENE (product of Arco Polymers, Inc.) andEXPANDABLE POLYSTYRENE BEADS (product of BASF Wyandote) as polystyreneballoons and SX863 (P) (product of Japan Synthetic Rubber Co.) ascrosslinked styrene-acrylic balloons.

The above balloons may be used independently or two or more species maybe used in admixture. Furthermore, these balloons may be used aftersurface-treating with a fatty acid, fatty acid ester, rosin, rhodinicacid lignin, a silane coupling agent, a titanium coupling agent, analuminum coupling agent or polypropylene glycol to improvedispersibility and workability of the composition. These balloons areused for the purpose of making the curing products light and reducingthe cost without deteriorating flexibility, elongation or strengthproperties among the physical properties when a mixture is subjected tocuring.

The balloon content is preferably in the range of about 0.1 to 50 parts,more preferably about 0.5 to 30 parts, relative in relation to 100 partsby weight of component (A1). If the content is less than 0.1 parts byweight, the effects of workability improvement maybe insufficient, whileif the content exceeds this range, tensile strength of the cured articlemay decrease, and recovery properties and durability may deteriorate.

In the present invention, as component (G), the aminosilane couplingagent represented by general formula (3):—SiR² _(a)(OR³)_(3-a)  (3)wherein a R² each are independent by a monovalent organic group having 1to 20 carbons, 3-a R³ each are independent by a monovalent organic grouphaving 2 to 20 carbons, and a represents 0, 1 or 2, can also be used.Adding this component (G) to the organic polymer having a grouprepresented by general formula (2) (the (A2) component of the presentinvention):—Si(OR¹)₃  (2)(wherein R¹ is the same as described above) provides for a curablecomposition which has excellent recovery properties, durability andcreep resistance, as well as exhibiting superior adhesion. Since thereactive silicon groups of this component (G) do not have a methoxygroup as the alkoxy group which is bonded to the silicon atom, even ifan ester exchange reaction progresses between component (G) and thereactive silicon group of component (A2) after the component (A2) hasbeen added, a highly reactive methoxysilyl group does not form in thereactive silicon group of component (A2). Therefore, the curing rate ofa curable composition which comprises the component (G) and thecomponent (A2) does not vary much between before and after storage. Inaddition, this reactive silicon group of both component (G) andcomponent (A2) provides a very safe compound, because the alkoxy groupbonded to the silicon atom has from 2 to 20 carbons, wherebyhighly-toxic methanol is not contained in the alcohol formed as a resultof the hydrolysis reaction of the reactive silicon group duringcondensation curing of the curable composition.

The above-described curable composition, which comprises a component (G)and a component (A2), can be used as one-part or as a multi-partcomposition, such as two-part, although a one-part composition has alarge effect on lowering the variation in curing rate between before andafter storage, and is thus more preferable.

Component (G) is a compound which comprises a reactive silicon grouprepresented by general formula (3) and an amino group. Specific examplesof the reactive silicon group represented by general formula (3) includetriethoxysilyl, methyldiethoxysilyl, dimethylethoxysilyl,ethyldiethoxysilyl, triisopropoxysilyl and methyldiisopropoxysilyl. Fromthe standpoint of the toxicity of the alcohol formed as a result of thehydrolysis reaction, the alkoxy group bonded to the silicon atom ispreferably ethoxysilyl or isopropxysilyl, ethoxysilyl being morepreferable. From the standpoint of curing rate, the number of alkoxygroups bonded to a single silicon atom of the reactive silicon group ispreferably not less than 2, and not less than 3 is more preferable. Fromthe standpoints of toxicity of the alcohol formed as a result of thehydrolysis reaction and curing rate, triethoxysilyl is the mostpreferable.

Specific examples of component (G) include amino group-containingsilanes such as γ-aminopropyltriethoxysilane,γ-aminopropyltriisopropoxysilane, γ-aminopropylmethyldiethoxysilane,γ-((β-aminoethyl)amino)propyltriethoxysilane,γ-((β-aminoethyl)amino)propyltriisopropoxysilane,γ-(β-aminoethyl)aminopropylmethyldiethoxysilane,γ-ureidopropyltriethoxysilane, γ-ureidopropyltriisopropoxysilane,γ-ureidopropylmethyldiethoxysilane,N-phenyl-γ-aminopropyltriethoxysilane,N-benzyl-γ-aminopropyltriethoxysilane,N-n-butyl-γ-aminopropyltriethoxysilane,N-vinylbenzyl-γ-aminopropyltriethoxysilane,N,N′-bis(γ-triethoxysilylpropyl) ethylenediamine,bis(triethoxysilylpropyl) amine,3-[2-(2-aminoethyl)aminoethyl]aminopropyltriethoxysilane and the like.In addition, derivatives in which the above-described silane compoundhas been modified and condensates of the above-described silanecompounds may also be used as component (G).

Component (G) is preferably used in a range from 0.1 to 10 parts andmore preferably from 1 to 5 parts, per 100 parts of the organic polymerof component (A2). Component (G) can be used alone or used incombination with two types or more.

A dehydrating agent may also be added when the component (A2) andcomponent (G)-containing composition is used as a one-part composition.Such a dehydrating agent is not particularly restricted, wherein variouscompounds may be employed. As the dehydrating agent, a silicon compoundwhich has an alkoxysilyl group and does not contain an amino group ispreferable, for the reasons that under aging at a comparatively lowtemperature, the change in properties before and after storage is small(because the ester exchange reaction between component (A2) and thereactive silicon group is slow), and that the dehydrating effects arehigh. A silicon compound which has a trialkoxysilyl group and does notcontain an amino group is preferable because it has a higher dehydratingeffect, and a silicon compound which has a trimethoxysilyl group anddoes not contain an amino group is particularly preferable. Specificexamples include alkyltrialkoxysilanes such as vinyltrimethoxysilane,methyltrimethoxysilane and phenyltrimethoxysilane, which are preferablein view of their dehydrating effect, curability, availability and curedarticle tensile properties.

In the present invention, as the component (H), the aminosilane couplingagent represented by general formula (4):—SiR⁴ _(b)(OCH₃)_(c)(OR⁵)_(3-b-c)  (4)wherein b R⁴ each are independent by a monovalent organic group having 1to 20 carbons, 3-a-c R⁵ each are independent by a monovalent organicgroup having 2 to 20 carbons, b represents 0, 1 or 2 and c represents 1,2 or 3 (3-b-c≧0), can be used. If a curable composition in which thiscomponent (H) has been added to an organic polymer having a grouprepresented by general formula (2) (the (A2) component of the presentinvention):—Si(OR¹)₃  (2)(wherein R¹ is the same as described above) is pre-aged, an esterexchange reaction proceeds between the methoxy group of component (H)and the reactive silicon group of component (A2), thus forming a highlyreactive methoxysilyl group in the reactive silicon group of component(A2). As a result, the yielded curable composition has excellentrecovery properties, durability and creep resistance, as well as being aquick-curing curable composition.

Although preferable aging conditions for the above-described curablecomposition comprising a component (H) and a component (A2) cannot becategorically defined, as they differ depending on the presence, andamount thereof, of an ester exchange reaction catalyst and the esterexchange reactivity between the component (H) and reactive silicon groupof component (A2) etc., if the ester exchange reaction catalyst contentin the system is about 0.5 to 3 parts of an organotin catalyst or aTi-based catalyst, aging for more than one week under comparativelylow-temperature conditions of 10 to 30° C. is preferable, while underhigh-temperature conditions of 30° C. and higher, aging for more thanone day is preferable.

The above-described curable composition, which comprises a component (H)and a component (A2), can be used as a one-part or a multi-partcomposition, such as two-part, although a one-part composition has theparticular advantage that the change in curing speed is dramatic, and isthus more preferable.

Component (H) is a compound which has a reactive silicon grouprepresented by general formula (4) and an amino group. Specific examplesof the reactive silicon group represented by general formula (4) includetrimethoxysilyl, methyldimethoxysilyl, ethyldimethoxysilyl,ethoxydimethoxysilyl, dimethylmethoxysilyl, diethylmethoxysilyl,diethoxymethoxysilyl and the like. The number of alkoxy groups bound toa single silicon atom of the reactive silicon group is preferably 2 ormore, and more preferably 3. A trimethoxysilyl group is therefore themost preferable.

Specific examples of component (H) include amino group-containingsilanes such as γ-aminopropyltrimethoxysilane,γ-aminopropylmethyldimethoxysilane, γ-aminopropylethyldimethoxysilane,γ-aminopropylethoxydimethoxysilane,γ-((β-aminoethyl)amino)propyltrimethoxysilane,γ-((β-aminoethyl)amino)propylmethyldimethoxysilane,γ-((β-aminoethyl)amino)propylethyldimethoxysilane,γ-((β-aminoethyl)amino)propylethoxydimethoxysilane,γ-ureidopropyltrimethoxysilane, γ-ureidopropylmethyldimethoxysilane,N-phenyl-γ-aminopropyltrimethoxysilane,N-benzyl-γ-aminopropyltrimethoxysilane,N-n-butyl-γ-aminopropyltrimethoxysilane,N-vinylbenzyl-γ-aminopropyltrimethoxysilane,N,N′-bis(γ-trimethoxysilylpropyl)ethylenediamine,bis(trimethoxysilylpropyl) amine,3-[2-(2-aminoethyl)aminoethyl]aminopropyltrimethoxysilane and the like.In addition, derivatives in which the above-described silane compoundhas been modified and condensates of the above-described silanecompounds may also be used as component (H)

Component (H) used in the present invention is preferably used in arange from 0.1 to 10 parts and more preferably from 1 to 5 parts, per100 parts of the organic polymer of component (A2). Component (H) can beused alone or used in combination with two types or more.

An epoxy resin can be used as the component (I) in the presentinvention. This epoxy resin not only improves the impact strength andtoughness of the component (A2) organic polymer of the presentinvention, but also has a function of further increasing recoveryproperties, durability and creep resistance.

As the epoxy resin used as component (I) in the present invention,widely-used epoxy resins can be employed, examples thereof includingepichlorohydrin-bisphenol A type epoxy resin, epichlorohydrin-bisphenolF type epoxy resin, flame retardant epoxy resins such as glycidyl etherof tetrabromobisphenol A; novolak type epoxy resin, hydrogenatedbisphenol A type epoxy resin, glycidyl ether type epoxy resin of abisphenol A propylene epoxide adduct, p-oxybenzoic acid glycidyl etherester type epoxy resin, m-aminophenol epoxy resin,diaminodiphenylmethane epoxy resin, urethane-modified epoxy resin,various alicyclic epoxy resins, N,N-diglycidylaniline,N,N-diglycidyl-o-toluidine, triglycidyl isocyanurate, polyalkyleneglycol diglycidyl ether, glycidyl ethers of polyvalent alcohol such asglycerin, hydantoin type epoxy resin, and epoxidated compounds ofunsaturated polymers such as a petroleum resin. The epoxy resin is notlimited to these examples. Among these epoxy resins, those having atleast two epoxy groups in the molecule are preferable because theresulting composition exhibits high reactivity upon curing and the curedarticle easily forms a three-dimensional network. More preferable epoxyresins are bisphenol A type epoxy resin and novolak type epoxy resin.The usage ratio between the epoxy resin (I) and the reactive silicongroup-containing organic polymer (A2) is within the range from 100/1 to1/100 parts by weight of (A2) to the epoxy resin. If the (A2)/epoxyratio is less than 1/100, the improvement in impact strength, toughness,properties, durability and creep resistance for the epoxy resin curedarticle cannot be achieved. If the (A2)/epoxy ratio is more than 100/1,the strength of the organic polymer cured article is insufficient.Although a preferable usage ratio cannot be categorically defined, as itdiffers depending on the intended use of the curable composition, if theimpact strength, flexibility, toughness, peeling strength and the likeof the epoxy resin cured article are to be improved, for example, usingfrom about 1 to 100 parts by weight of component (A2) in relation to 100parts by weight of the epoxy resin is preferable, and more preferable isfrom 5 to 100 parts by weight. In the case of improving the strength ofthe component (A2) cured article, using from about 1 to 200 parts byweight of the epoxy resin in relation to 100 parts by weight ofcomponent (A2) is preferable, more preferable is from 5 to 100 parts byweight, and particularly preferable is from 5 to 50 parts by weight.

It is obvious that in the composition of the present invention, a curingagent for curing the epoxy resin can be used in combination. The epoxyresin curing agent which can be used is not particularly restricted, andthus a conventionally used epoxy resin curing agent may be employed.Specific examples include primary and secondary amines, such astriethylenetetramine, tetraethylenepentamine, diethylaminopropylamine,N-aminoethylpiperazine, m-xylylenediamine, m-phenylenediamine,diaminodiphenylmethane, diaminodiphenylsulfone, isophoronediamine, andan amine-terminated polyether; tertiary amines and the salts thereof,such as 2,4,6-tris(dimethylaminomethyl)phenol and tripropylamine;polyamide resins; imidazoles; dicyandiamides; boron trifluoride complexcompounds; carboxylic anhydrides such as phthalic anhydride,hexahydrophthalic anhydride, tetrahydrophthalic anhydride,dodecenylsuccinic anhydride, pyromellitic anhydride, and curorenicanhydride; alcohols; phenols; carboxylic acids; and diketone complexcompounds of aluminum or zirconium. The epoxy resin curing agent is notlimited to these examples. The curing agent can be alone or incombination of two types or more.

When using a curing agent for the epoxy resin, the content should be inthe range from about 0.1 to 300 parts by weight in relation to 100 partsby weight of the epoxy resin.

A ketimine may be used as the curing agent for the epoxy resin.Ketimines stably exist in conditions free from moisture, and react withmoisture and decompose to a primary amine, wherein the formed primaryamine can serve as a room temperature-curable curing agent for the epoxyresin. If a ketimine is used, a one-part compound can be achieved. Suchketimines can be obtained from the condensation reaction of an aminecompound with a carbonyl compound.

Known amine compounds and carbonyl compounds can be used for theketimine synthesis. Examples of the amine compound that can be usedinclude diamines such as ethylenediamine, propylenediamine,trimethylenediamine, tetramethylenediamine, 1,3-diaminobutane,2,3-diaminobutane, pentamethylenediamine, 2,4-diaminopentane,hexamethylenediamine, p-phenylenediamine and p,p′-biphenylenediamine;polyvalent amines, such as 1,2,3-triaminopropane, triaminobenzene,tris(2-aminoethyl)amine and tetra(aminomethyl)methane;polyalkylenepolyamines, such as diethylenetriamine, triethylenetriamineand tetraethylenepentamine; polyoxyalkylene-based polyamines; andaminosilanes, such as γ-aminopropyltriethoxysilane,N-(β-aminoethyl)-γ-aminopropyltrimethoxysilane andN-(β-aminoethyl)-γ-aminopropylmethyldimethoxysilane. Examples of thecarbonyl compound that can be used include aldehydes such asacetylaldehyde, propionaldehyde, n-butylaldehyde, isobutylaldehyde,diethylacetaldehyde, glyoxal and benzaldehyde; cyclic ketones, such ascyclopentanone, trimethylcyclopentanone, cyclohexanone andtrimethylcyclohexanone; aliphatic ketones, such as acetone, methylethylketone, methylpropyl ketone, methylisopropyl ketone, methylisobutylketone, diethyl ketone, dipropyl ketone, diisopropyl ketone,dibutylketone and diisobutyl ketone; and β-dicarbonyl compounds, such asacetylacetone, methyl acetoacetate, ethyl acetoacetate, dimethylmalonate, diethyl malonate, methylethyl malonate and dibenzoylmethane.

When an imino group is present in the ketimine, the imino group may bereacted with styrene oxide; a glycidyl ether such as butyl glycidylether and allyl glycidyl ether; and glycidyl ester. These ketimines maybe used alone or in combination of two kinds or more. The ketamines maybe used from 1 to 100 parts by weight in relation to 100 parts by weightof the epoxy resin, although the content will depend on the epoxy resinand the type of ketimine.

In the present invention, an aminosilane coupling agent can be furtheradded. While it is known that the addition of an aminosilane couplingagent generally improves the adhesion of the compound, such addition canalso have the effect of lowering the recovery properties, durability andcreep resistance of the obtained cured article. If an amino silanecoupling agent is added to the composition of the present invention,adhesion can coexist with recovery properties, durability and creepresistance, and is thus preferable.

Specific examples of the aminosilane coupling agent include the samecompounds as those described above as the specific examples forcomponent (G) and component (H).

The content of the aminosilane coupling agent is preferably from about0.1 to 10 parts by weight in relation to 100 parts by weight ofcomponent (A1), and more preferably from about 1 to 5 parts by weight.If the amount is lower than this range, the adhesion improvement effectsmay not be sufficient, while if the amount is higher than this range,extension of the cured article can be reduced, and the recoveryproperties and durability may deteriorate.

The curable composition according to the present invention can serve asa one-part curable composition through the further addition of adehydrating agent. Since a dehydrating agent-containing one-part curablecomposition does not need to undergo a mixing operation, it is a moreconvenient material than a two-part composition. However, because aone-part curable composition cures from its surface due to moisture inthe atmosphere, curing of the entire sealing material requires a longtime, wherein deep crosslinking is insufficient and the recoveryproperties and durability may deteriorate. If a one-part composition isused by adding a dehydrating agent to the composition of the presentinvention, the convenience of a one-part composition can coexist withrecovery properties, durability and creep resistance, and is thuspreferable.

Specific examples of the dehydrating agent, while not particularlyrestricted, include alkyl orthoformates, such as methyl orthoformate andethyl orthoformate, alkyl orthoacetates, such as methyl orthoacetate andethyl orthoacetate, and hydrolyzable organic silicon compounds, such asvinyltrimethoxysilane and methyltrimethoxysilane. In view of cost andeffects, vinyltrimethoxysilane and methyltrimethoxysilane areparticularly preferable.

The content of the dehydrating agent is preferably from about 0.1 to 10parts by weight in relation to 100 parts by weight of component (A1),and more preferably from about 1 to 5 parts by weight. If the amount islower than this range, the dehydrating effects may not be sufficient,while if the amount is higher than this range, the extension of thecured article and deep-part curability may deteriorate.

Various fillers other than the component (F) balloons may be mixed intothe curable composition of the present invention. Such fillers are notparticularly restricted, but include reinforcing fillers such as fumedsilica, precipitated silica, silicic anhydride, hydrous silicic acid,carbon black and the like; fillers such as calcium carbonate, magnesiumcarbonate, diatomaceous earth, calcined clay, clay, talc, titaniumoxide, bentonite, organic bentonite, ferric oxide, zinc oxide, activatedzinc white, hydrogenated castor oil and the like; and fibrous fillerssuch as asbestos, glass fibers or filaments and the like.

When high-strength curable compositions are desired using these fillers,preferable effects can be obtained by mainly employing a filler selectedfrom among fumed silica, precipitated silica, silicic anhydride, hydroussilicic acid, carbon black, surface-treated fine calcium carbonate,calcined clay, clay and activated zinc white, etc. in the range from 1to 100 parts by weight in relation to 100 parts by weight of the organicpolymer (A). When low-strength high-elongation curable compositions aredesired, preferable effects can be obtained by mainly using a fillerselected from among titanium oxide, calcium carbonate, magnesiumcarbonate, talc, ferric oxide and zinc oxide etc. in the range from 5 to200 parts by weight in relation to 100 parts by weight of the organicpolymer (A). Needless to say, a single filler may be used alone or twoor more fillers may be used in combination.

In the curable composition of the present invention, it is moreeffective to use a plasticizer in combination with a filler because itis possible to enhance elongation of the cured article and to mix alarge amount of the filler.

Specific examples of a plasticizer include phthalic acid esters such asdioctyl phthalate, dibutyl phthalate and butylbenzyl phthalate;aliphatic dibasic acid esters such as dioctyl adipate, isodecylsuccinate, and dibutyl sebacate; glycol esters such as diethylene glycoldibenzoate and pentaerythritol ester; aliphatic esters such as butyloleate and methyl acetylricinoleate; phosphoric acid esters such astricresyl phosphate, trioctyl phosphate, and octyldiphenyl phosphate;epoxy plasticizers such as epoxidated soybean oil, epoxidated linseedoil, and benzyl epoxystearate; polyester plasticizers such as polyestersof dibasic acid and a divalent alcohol; polyethers such as polypropyleneglycol and its derivatives; polystyrenes such as poly-α-methylstyreneand polystyrene; and polybutadiene, butadiene-acrylonitrile copolymer,polychloroprene, polyisoprene, polybutene, chlorinated paraffins and thelike.

In addition, high-molecular weight plasticizers can also be used.Compared with when using a low-molecular weight plasticizer that doesnot contain a polymer component in the molecule, the use of ahigh-molecular weight plasticizer enables the initial physicalproperties to be maintained over a long period of time, and improves thedryability (also referred to as “coatability”) when an alkyd coating isapplied to said curing article. Specific examples of such high-molecularweight plasticizer include, but are not limited to, vinyl polymersobtainable by polymerizing a vinyl monomer by various methods;polyalkylene glycol esters such as diethylene glycol dibenzoate,triethylene glycol dibenzoate and pentaerythritol esters; polyesterplasticizers obtainable from a dibasic acid, such as sebacic acid,adipic acid, azelaic acid or phthalic acid, and a dihydric alcohol, suchas ethylene glycol, diethylene glycol, triethylene glycol, propyleneglycol or dipropylene glycol; polyethers such as polyether polyols, e.g.polyethylene glycol, polypropylene glycol and polytetramethylene glycolthat have a molecular weight of 500 or more, and even further 1,000 ormore, and derivatives of these as obtainable by converting the hydroxylgroups of these polyether polyols to an ester, ether or the like groups;polystyrenes such as polystyrene and poly-α-methylstyrene;polybutadiene, polybutene, polyisobutylene, butadiene-acrylonitrile,polychloroprene and the like.

Among these high-molecular-weight plasticizers, those compatible withcomponent (A) are preferred. Polyethers and vinyl polymers arepreferred. Among them, vinyl polymers are preferred in view ofcompatibility, weatherability and heat resistance. Among vinyl polymers,acrylic or methacrylic polymers are preferred, and acrylic polymers suchas polyalkyl acrylate ester are more preferred. For the method ofsynthesizing such polymers, living radical polymerization is preferable,since this method makes it possible to narrow the molecular weightdistribution of the polymer and reduce the viscosity. Further, atomtransfer radical polymerization is more preferred. It is preferable touse a polymer obtained from continuous mass polymerization (so-called“SGO process”) under high-temperature high-pressure of an alkyl acrylateester monomer disclosed in Japanese Patent Publication No. 2001-207157.

The number average molecular weight of the high-molecular-weightplasticizer is preferably from 500 to 15,000, more preferably from 800to 10,000, still more preferably from 1,000 to 8,000, particularlypreferably from 1,000 to 5,000, and most preferably from 1,000 to 3,000.If the molecular weight is too low, the plasticizer will leak out overtime due to heat and precipitation, whereby the initial physicalproperties cannot be maintained for a long period of time and nor canthe alkyd coatability be improved. If the molecular weight is too high,viscosity becomes high and workability deteriorates. Although themolecular weight distribution of the high-molecular weight plasticizeris not particularly restricted, a narrow distribution is preferable,less than 1.80 being preferable, 1.70 or less more preferable, 1.60 orless still more preferable, 1.50 or less especially preferable, and 1.30or less the most preferable.

The number average molecular weight of the high-molecular-weightplasticizer and the molecular weight distribution (Mw/Mn) were measuredusing a GPC method (polystryrene conversion).

While the high-molecular-weight plasticizer may be without a reactivesilicon group, it may contain a reactive silicon group. When thehigh-molecular-weight plasticizer does contain a reactive silicon group,it can act as a reactive plasticizer, thereby preventing the movement ofa plasticizer from the cured article. When the high-molecular-weightplasticizer contains a reactive silicon group, an average of not morethan 1 group per molecule is preferable, and not more than 0.8 is morepreferable. When a reactive silicon group-containinghigh-molecular-weight plasticizer, especially a reactive silicongroup-containing oxyalkylene polymer, is used, its number averagemolecular weight must be lower than that of the component (A) polymer.

The plasticizer may be used alone or in combination of 2 types or more.A combination of a low-molecular-weight plasticizer and ahigh-molecular-weight plasticizer can also be used. These plasticizerscan be mixed in when the polymer is produced.

The amount of a plasticizer is preferably from 5 to 150 parts by weight,more preferably from 10 to 120 parts by weight, and still morepreferably from 20 to 100 parts by weight in relation to 100 parts byweight of component (A). When the amount of a plasticizer is less than 5parts by weight, the effects as a plasticizer may not be expressed,while more than 150 parts by weight and the mechanical strength of thecured article are insufficient.

In the curable composition according to the present invention, thesilicon compound represented by the general formula R²⁰_(h)Si(OR²¹)_(4-h) (wherein R²⁰ and R²¹ are each independent bysubstituted or unsubstituted hydrocarbons having 1 to 20 carbons; and hrepresents 0, 1, 2 or 3) may be added to increase the activity of thecondensation catalyst. While this silicon compound is not restricted, ageneral formula in which R is an aryl group having 6 to 20 carbons, suchas phenyltrimethoxysilane, phenylmethyldimethoxysilane,phenyldimethylmethoxysilane, diphenyldimethoxysilane,diphenyldiethoxysilane and triphenylmethoxysilane, is preferred sinceits accelerating effect on the curing reaction of the composition issignificant. In particular, diphenyldimethoxysilane anddiphenyldiethoxysilane are inexpensive and easily available, and henceare most preferred. The amount of this silicon compound is preferablyabout 0.01 to 20 parts, more preferably 0.1 to 10 parts, relative inrelation to 100 parts of component (A). When the amount of addition isbelow this range, the curing reaction-accelerating effect may decreasein some cases. When, conversely, the amount of addition of the siliconcompound exceeds this range, the hardness and/or tensile strength of thecuring products may fall.

A physical property modifier may be added to the curable composition ofthe present invention according to need for adjusting the tensileproperties of the resulting cured article. The physical propertymodifier is not particularly restricted but includes, for example,alkylalkoxysilanes such as methyltrimethoxysilane,dimethyldimethoxysilane, trimethylmethoxysilane andn-propyltrimethoxysilane; functional group-containing alkoxysilanes, forexample alkylisopropenoxysilanes such as dimethyldiisopropenoxysilane,methyltriisopropenoxysilane andγ-glycidoxypropylmethyldiisopropenoxysilane,γ-glycidoxypropylmethyldimethoxysilane,γ-glycidoxypropyltrimethoxysilane, vinyltrimethoxysilane,vinyldimethylmethoxysilane, γ-aminopropyltrimethoxysilane,N-(β-aminoethyl)aminopropylmethyldimethoxysilane,γ-mercaptopropyltrimethoxysilane andγ-mercaptopropylmethyldimethoxysilane; silicone varnishes; andpolysiloxanes. Using the above-described physical property modifierenables the hardness to be increased or decreased and/or elongationproperties to be attained upon curing of the composition of theinvention. The above-described physical property modifies may be usedalone or two or more types may be used in combination.

Especially, a compound which forms a monovalent silanol group-containingcompound within the molecule from hydrolysis acts to reduce the modulusof the cured article without a deterioration in the cured articlesurface stickiness. In particular, a compound which formstrimethylsilanol is preferable. Examples of compounds which forms amonovalent silanol group-containing compound within the molecule fromhydrolysis include those disclosed in Japanese Patent Publication No.5-117521. Further examples include alkyl alcohol derivatives, such ashexanol, octanol and decanol, which form a silicon compound representedby the general formula R²² ₃SiOH (wherein R²² are each independent bysubstituted or unsubstituted hydrocarbons having 1 to 20 carbons), suchas trimethylsilanol from hydrolysis; and polyvalent alcohol derivativeshaving at least 3 hydroxyl groups, such as trimethylolpropane, glycerin,pentaerythritol or sorbitol disclosed in Japanese Patent Publication No.11-241029, which form a silicon compound represented by the generalformula R²² ₃SiOH (wherein R²² are the same as described above) such astrimethylsilanol from hydrolysis.

Additional examples include oxypropylene polymer derivatives such asthose disclosed in Japanese Patent Publication No. 7-258534, which forma silicon compound represented by the general formula R²² ₃SiOH (whereinR²² are the same as described above), such as trimethylsilanol fromhydrolysis. Still further, silicon group-containing polymers that arecapable of turning into a monosilanol-containing compound fromhydrolysis of the crosslinkable hydrolyzable silicon-containing groupsdisclosed in Japanese Patent Publication No. 6-279693 can be used.

The physical property modifier can be used in the range from 0.1 to 20parts by weight, and preferably from 0.5 to 10 parts by weight, relativein relation to 100 parts by weight of component (A).

A thixotropy imparting agent (antisagging agent) may be added to thecurable composition of the present invention according to need forsagging prevention and workability improvement. The antisagging agent isnot particularly restricted but includes, for example, polyamide waxes;hydrogenated castor oil derivatives; and metal soaps such as calciumstearate, aluminum stearate and barium stearate. These thixotropyimparting agents (antisagging agents) may be used singly or two or moreof them may be used in combination. The thixotropy imparting agent canbe used in the range from 0.1 to 20 parts by weight relative in relationto 100 parts by weight of component (A).

In the composition of the present invention, a compound which containsan epoxy group in a molecule can be used. If an epoxy group-containingcompound is used, the recovery properties of the cured article can beincreased. Examples of epoxy group-containing compounds includeepoxidized unsaturated fats, epoxidized unsaturated fatty acid esters,alicyclic epoxidized compounds and compounds shown in epichlorohydrinderivatives and mixtures thereof. Specific examples include epoxidizedsoybean oil and epoxidized linseed oil,di-(2-ethylhexyl)4,5-epoxycyclohexane-1,2-dicarboxylate (E-PS), epoxyoctyl stearate and epoxy butyl stearate. Among these E-PS isparticularly preferable. The epoxy compound can be used in the rangefrom 0.5 to 50 parts by weight relative in relation to 100 parts byweight of component (A).

In the composition of the present invention, an oxidation-curablesubstance can be used. The air oxidation-curable substance includesunsaturated compounds capable of reacting with oxygen in the air, whichreact in the air to form a cured skin close to the surface of the curedarticle for preventing surface stickiness and dirt and dust fromadhering to the cured article surface. Specific examples of the airoxidation-curable substance include, for example, dry oils such as tungoil and linseed oil; various alkyd resins obtainable by modification ofsuch dry oils; acrylic polymers, epoxy resins and silicone resins eachmodified by a drying oil; liquid polymers, such as 1,2-polybutyldiene,1,4-polybutyldiene and the polymers of C5 to C8 dienes, obtainable bypolymerizing or copolymerizing diene compounds such as butadiene,chloroprene, isoprene and 1,3-pentadiene, NBR, SBR and like polymersobtainable by copolymerizing such diene compounds with a monomercopolymerizable with the diene compounds, for example acrylonitrile orstyrene, in a manner such that the diene compounds account for themajority and, further, various modifications (maleic modifications,boiled oil modifications, etc.) thereof. These may be used singly or twoor more of them may be used in combination. Among these compounds, tungoil and liquid diene polymers are particularly preferred. In some cases,the use of the air oxidation-curable substance together with a catalystor metal drier capable of promoting the oxidation/curing reactions maybring about enhanced effects. As such catalyst or metal drier, there maybe mentioned, for example, cobalt naphthenate, lead naphthenate,zirconium naphthenate, cobalt octylate, zirconium octylate and likemetal salts as well as amine compounds. The air oxidation-curablesubstance is added preferably in an amount of 0.1 to 20 parts by weight,more preferably 0.5 to 10 parts by weight, relative in relation to 100parts by weight of component (A). If the amount is less than 0.1 partsby weight, the improvement in staining are insufficient and, if it is inexcess of 20 parts by weight, there is a tendency for the tensileproperties of the cured article to be adversely affected. As disclosedin Japanese Patent Publication No. 3-160053, the oxidation-curablesubstance is preferably used in combination with a photocurablesubstance.

In the composition of the present invention, a photocurable substancecan be used. If a photocurable substance is used, a photocurablesubstance skin forms on the surface of the cured article, which canimprove the stickiness and the weatherability of the cured article. Thephotocurable substance is a substance which, under the action of light,undergoes chemical changes in molecular structure in a short period oftime, leading to curing and other changes in physical properties. Anumber of compounds of this kind are known, including organic monomers,oligomers, resins, and compositions containing them. Acommercially-available compound can be employed, representative examplesincluding an unsaturated acrylic compound, a polyvinyl cinnamate or anazide resin. Examples of the unsaturated acrylic compound include amonomer or oligomer containing one or more acrylic or methacrylicunsaturated groups, or a mixture thereof, for example monomers such aspropylene (or butylene or ethylene) glycol di(meth)acrylate, neopentylglycol di(meth)acrylate, or oligo esters having a molecular weight of10,000 or less. Specific examples include the particular acrylates(bifunctional) Aronix M-210, Aronix M-215, Aronix M-220, Aronix M-233,Aronix M-240 and Aronix M-245; (trifunctional) Aronix M-305, AronixM-309, Aronix M-310, Aronix M-315, Aronix M-320 and Aronix M-325;(polyfunctional) Aronix M-400 and the like. Compounds which contain anacryl group are preferable, which compounds contain an average of 3 ormore of the same functional group per molecule being preferable. (Theabove-described Aronix products are all manufactured by Toa GoseiChemical Industries.)

The polyvinyl cinnamate is a photosensitive resin whose cinnamoyl groupsserve as photosensitive groups. It includes cinnamic acid-esterifiedpolyvinyl alcohol and, further, various polyvinyl cinnamate derivatives.The azide resin is known as a photosensitive resin whose azide groupsserve as photosensitive groups. It includes photosensitive rubbersolutions generally containing an azide compound as a photosensitiveagent and, further, various examples are described in detail in themonograph “Kankosei Jushi (Photosensitive Resins)” (published Mar. 17,1972 by Insatsu Gakkai Shuppanbu, page 93 ff, page 106 ff and page 117ff). These can be used singly or in admixture, and if necessarysupplemented with a sensitizer. In some cases, the addition of asensitizer, such as a ketone or nitro compound, and/or a promoter, suchas an amine, may result in enhanced effects. The photocurable substanceis used in an amount of 0.1 to 20 parts by weight, and preferably 0.5 to10 parts by weight, per 100 parts by weight of component (A). If theamount is less than 0.1 parts by weight, there is no increase inweatherability and, when it exceeds 20 parts by weight, the curedarticle becomes too hard, which is not preferable since cracks may form.

An antioxidant (anti-aging agent) can be used in the composition of thepresent invention. If an antioxidant is used, the heat resistance of thecured article can be increased. Examples of the antioxidant includehindered phenols, monophenols, bisphenols and polyphenols, althoughhindered phenols are preferable. Examples which can be used as thehindered-amine photostabilizer include TINUVIN 622LD, TINUVIN 144,CHIMASSORB 944LD, CHIMASSORB 119FL (all being products of Ciba SpecialtyChemicals); Adeka Stab LA-57, Adeka Stab LA-62, Adeka Stab LA-67, AdekaStab LA-63 and Adeka Stab LA-68 (all being products of Asahi Denka Co.,Ltd.); Sanol LS-770, Sanol LS-765, Sanol LS-292, Sanol LS-2626, SanolLS-1114 and Sanol LS-744 (all being products of Sankyo Co.), and thelike. Specific examples of the antioxidant agent are also disclosed inJapanese Patent Publication Nos. 4-283259 and 9-194731. The amount ofantioxidant is preferably in the range from 0.1 to 10 parts by weight,and more preferably 0.2 to 5 parts by weight, per 100 parts by weight ofcomponent (A).

A photostabilizer can be used in the composition of the presentinvention. If a photostabilizer is used, photo-oxidation of the curedarticle can be prevented. Examples of the photostabilizer includebenzotriazoles, hindered amines and benzoate compounds, althoughhindered amines are preferable. The amount of photostabilizer ispreferably in the range from 0.1 to 10 parts by weight, and morepreferably 0.2 to 5 parts by weight, per 100 parts by weight ofcomponent (A). Specific examples of the photostabilizer are alsodisclosed in Japanese Patent Publication No. 9-194731.

In the composition of the present invention, particularly when anunsaturated acrylic compound is used as the photocurable substance, forreasons of storage stability improvement of the compound it ispreferable to use a hindered-amine-containing photostabilizer whichcontains a tertiary amine as the hindered amine photostabilizer, asdisclosed in Japanese Patent Publication No. 5-70531. Examples of atertiary amine-containing hindered amine photostabilizer include TINUVIN622LD, TINUVIN 144, CHIMASSORB 119FL (all being products of CibaSpecialty Chemicals); Adeka Stab LA-57, Adeka Stab LA-62, Adeka StabLA-67 and Adeka Stab LA-63 (all being products of Asahi Denka Co.,Ltd.); Sanol LS-765, Sanol LS-292, Sanol LS-2626, Sanol LS-1114 andSanol LS-744 (all being products of Sankyo Co.) and the like.

An ultraviolet absorber can be used in the composition of the presentinvention. If an ultraviolet absorber is used, the surfaceweatherability of the cured article can be increased. Examples of theultraviolet absorber include benzophenones, benzotriazoles, salicylates,substituted trioles and metal chelate compounds, although benzotriazolesare preferable. The amount of ultraviolet absorber is preferably in therange from 0.1 to 10 parts by weight, and more preferably 0.2 to 5 partsby weight, per 100 parts by weight of component (A). The benzotriazoleultraviolet absorber is preferably used in combination with a phenol orhindered phenol antioxidant and a hindered amine photostabilizer.

The method of preparing the curable composition of the present inventionis not particularly restricted and, for example, there can be used amethod of mixing the above-described components, kneading the mixture atnormal temperature or elevated temperature using a mixer, roll, kneaderor the like, or a method of dissolving the components in a small amountof a proper solvent and mixing. By appropriately using these componentsin combination, one-part and multi-part, such as two-part, compositionscan be prepared and used.

When the curable composition of the present invention is exposed toatmospheric air, it forms a three-dimensional network by the action ofmoisture in the atmospheric air and thus rapidly cures into a solidhaving rubber elasticity.

To the curable composition of the present invention, various additivescan be added, if necessary. Examples of such additives include adhesionimparting agents other than aminosilanes, storage stabilizers, metaldeactivators, antiozonants, amine type radical chain inhibitors,phosphorus peroxide decomposing agents, lubricants, pigments and blowingagents.

The curable composition of the invention can be used in tackifiers,sealants for buildings, ships, motor vehicles, roads, and so on,adhesives, mold extrusion agents, vibration absorbers, dampeningmaterials, sound insulating materials, foaming materials, paint andgunning materials. The curable composition of the invention can befurther used in a variety of applications, for example electric andelectronic part materials such as solar cell reverse side sealingmaterials; electric insulating materials such as insulating coveringmaterials for electric wires and cables, elastic adhesives, powdercoatings, casting materials, rubber materials for medical use, adhesivesfor medical use, device sealants for medical use, food packagingmaterials and exterior seam sealing materials such as siding boards;coating materials, primers, electromagnetic shielding conductivematerials, thermally conductive materials, hot melt materials, pottingagents for electric and electronic use, films, gaskets, various moldingmaterials, and rustproof/waterproof sealants for terminal faces (cutsections) of wire glass or double glazing, and liquid sealants used inautomotive parts, electric machinery parts and various other machineryparts. Furthermore, either used alone or with the aid of a primer, thecomposition is capable of adhering intimately to a large variety ofadherends inclusive of shaped articles of glass, porcelain, ceramics,wood, metal or resin, and thus the composition can be applied to asealing composition or an adhesive composition in many different fields.Since the curable composition of the present invention has excellentcreep resistance, it can be preferably used as a panel adhesive such asan interior panel adhesive, an exterior panel adhesive, a tile hangingadhesive, a stone hanging adhesive, an automotive panel adhesive and thelike. Among these, using the present composition as an automotive paneladhesive is especially preferable, because of the high creep resistancedemanded. Moreover, since the curable composition of the presentinvention is excellent in recovery properties and durability, it can bepreferably used as a sealing material for the working joints of abuilding (coping, periphery of window glass, periphery of windowframe/window sash, curtain walls and various exterior panels). Thelarger the displacement of a seam, the larger the elongation of asealing material can be. Therefore, the curable composition of thisinvention achieves remarkable effect when the displacement of a seam islarge. Therefore, the present composition is preferably used in a seamwherein the ratio of the displacement width to the average width is 10%or greater, more preferably used in a seam of 15% or greater, andespecially preferably used in a seam of 20% or greater.

EXAMPLES

The present invention will now be further described using Examples andComparative Examples. However, these Examples and Comparative Examplesare by no means meant to limit the scope of the present invention.

Synthesis Example 1

Using polyoxypropylenetriol having a molecular weight of about 3,000 asan initiator, propyleneoxide was polymerized in the presence of a zinchexacyanocobaltate glyme complex catalyst to obtain polypropylene oxidehaving a number average molecular weight of about 26,000 (molecularweight relative to polystyrene standards as measured by using aHLC-8120GPC manufactured by Tosoh Corporation as the liquid deliverysystem, using a TSK-GEL H-type column manufactured by Tosoh Corporationas the column, and using THF as the solvent). Subsequently, a methanolsolution of NaOMe was added in the amount of 1.2 equivalent mol perequivalent mol of the hydroxyl group of the hydroxyl-terminatedpolypropyl eneoxide. The methanol was distilled off and allyl chloridewas further added to convert the terminal hydroxyl group into an allylgroup. Unreacted allyl chloride was removed by reduced-pressureevaporation. In relation to 100 parts by weight of the obtained crudeallyl-terminated polypropylene oxide, 300 parts by weight of n-hexaneand 300 parts by weight of water were mixed while stirring. The waterwas then removed by centrifugal separation. Once again, 300 parts byweight of water were added with stirring, and removed by centrifugalseparation. Hexane was then removed by reduced-pressure evaporation, tothereby obtain an allyl-terminated trifunctional polypropylene oxidehaving a number average molecular weight of about 26,000.

Using an isopropanol solution of platinum divinyldisiloxane complex of 3wt. % in terms of platinum as a catalyst, in 150 ppm 1.4 parts by weightof methyldimethoxysilane were reacted with 100 parts by weight of theobtained allyl-terminated trifunctional polypropylene oxide at 90° C.for 5 hours, to thereby obtain a methyldimethoxysilyl-terminatedpolyoxypropylene polymer (A-1). The terminal methyldimethoxysilyl groupswere present in an average of 2.3 groups per molecule as measured by¹H-NMR (measured in a CDCl₃ solvent using JNM-LA400 manufactured byJEOL).

Examples 1 to 4 and Comparative Examples 1 and 2

Added together in accordance with the mixing formulation shown in Table1 were 100 parts by weight of the reactive silicon group-containingorganic polymer (A-1) obtained in Synthesis Example 1, 120 parts byweight of surface-treated precipitated calcium carbonate (manufacturedby Shiraishi Kogyo Co., Ltd. under the trade name of HAKUENKA CCR), 20parts by weight of titanium oxide (manufactured by Ishihara SangyoKaisha, Ltd., under the trade name of Tipaque R-820), 55 parts by weightof a plasticizer diisodecyl phthalate (manufactured by New JapanChemical Co., Ltd., under the trade name SANSOCIZER DIDP), 2 parts byweight of a thixotropy imparting agent (manufactured by KusumotoChemicals, Ltd., under the trade name Disparlon 6500), 1 part by weightof a photostabilizer (manufactured by Sankyo Co., Ltd. under the tradename of Sanol LS-770), 1 part by weight of an ultraviolet absorber(manufactured by Ciba Specialty Chemicals, under the trade name ofTINUVIN 327), 1 part by weight of an antioxidant (manufactured by OuchiShinko Chemical Industrial Co., Ltd., under the trade name Nocrac SP), 2parts by weight of the dehydrating agent vinyltrimethoxysilane(manufactured by Nippon Unicar Co., Ltd. under the trade name of A-171),3 parts by weight of an adhesion-imparting agentN-(β-aminoethyl)-γ-aminopropyltrimethoxysilane (manufactured by NipponUnicar Co., Ltd. under the trade name of A-1120), 2 parts by weight ofthe silicates shown in Table 1 (trade names Ethyl Silicate 28; EthylSilicate 40; and Methyl Silicate 51, all manufactured by Colcoat Co.,Ltd.) and the curing catalyst as shown in Table 1, in the amount shownin Table 1 (dibutyltin bisacetylacetonate (manufactured by Nitto KaseiCo., Ltd. under the trade name of U-220); tin neodecanoate (divalent)(manufactured by Nitto Kasei Co., Ltd. under the trade name of U-50);neodecanoic acid (manufactured by Japan Epoxy Resins Co., Ltd., underthe trade name of Versatic 10); and laurylamine (manufactured by WakoPure Chemical Industries, Ltd.) The resultant mixture was kneaded underdehydrating conditions in a state in which the mixture was essentiallyfree from water, then sealed into a moisture-proof container to obtain aone-part curable composition.

(Tensile Properties of the Cured Article)

Each of the compositions of Table 1 was aged at 23° C. for 3 days and at50° C. for 4 days to prepare a sheet which was 3 mm in thickness. Thissheet was stamped out by No. 3 dumbbell-shaped dies, and the dumbbellspecimen was subjected to a tensile test at a tensile rate of 200 mm perminute for measuring the M50: 50% tensile modulus (MPa) Tb: tensilestrength at break (MPa) and Eb: the elongation at break (%). Results areshown in Table 1.

(Recovery Ratio)

Each of the compositions of Table 1 was aged at 23° C. for 3 days and at50° C. for 4 days to prepare sheets which were about 3 mm in thickness.These sheets were stamped out by No. 3 dumbbell-shaped dies, and thedumbbell specimens were fixed for 24 hours at 60° C. in a state in which20 mm token line intervals were stretched to 40 mm (100% elongation).These dumbbell specimens were released at 23° C., whereby the recoveryratio was determined from the ratio that the token line had recoveredafter 1 hour. A greater recovery ratio indicated superior recoveryproperties. Results are shown Table 1.

(Creep Measurement Employing a Dumbbell Specimen)

Each of the compositions of Table 1 was aged at 23° C. for 3 days at 50°C. for 4 days to prepare sheets which were about 3 mm in thickness.These sheets were stamped out by No. 3 dumbbell-shaped dies, and thedumbbell specimens were marked with a token line at 20 mm intervals. Oneterminal of this dumbbell specimen was fixed in an oven at 60° C.,whereby the dumbbell specimen was made to hang down. A load of 0.4 timesthe M50 value obtained from the above-described tensile propertiesmeasurement for the subject cured article was placed onto the lowerterminal of the hanging-down dumbbell specimen. The displacementdifference of the token line interval distances between immediatelyafter the load was placed and 200 hours after the load was placed wasmeasured. A smaller displacement difference indicated superior recoveryproperties. Results are shown in Table 1. TABLE 1 Comparative ExampleExample Composition (parts by weight) 1 2 3 4 1 2 Organic Component A-1100 100 100 100 100 100 Polymer (A) Filler HAKUENKA CCR 120 120 120 120120 120 Tipaque R-820 20 20 20 20 20 20 Plasticizer SANSOCIZER 55 55 5555 55 55 DIDP Thixotropy Imparting Disparlon 2 2 2 2 2 2 Agent #6500Photostabilizer Sanol LS-770 1 1 1 1 1 1 Ultraviolet Absorber TINUVIN327 1 1 1 1 1 1 Antioxidant Nocrac SP 1 1 1 1 1 1 Dehydrating AgentA-171 2 2 2 2 2 2 Adhesion-imparting A-1120 3 3 3 3 3 3 agent SilicateComponent Ethyl Silicate 2 2 (B) 28 Ethyl Silicate 2 40 Methyl 2Silicate 51 Curing Organotin Neostann U-220 2 2 Catalyst Tin NeostannU-50 3.4 3.4 3.4 3.4 carboxylate Carboxylic Versatic 10 1.2 1.2 1.2 1.2Acid Amine Laurylamine 0.75 0.75 0.75 0.75 Recovery Ratio (%) 54 84 8886 26 80 Creep (mm) 15.1 1.6 1.2 1.4 30.2 2.2 Cured M50 (MPa) 0.53 0.460.48 0.50 0.42 0.43 Article Tb (MPa) 2.00 2.27 2.61 2.35 1.96 2.23Properties Eb (%) 297 400 442 389 385 480

As illustrated in Comparative Example 1 of Table 1, when organotin(U-220) was used as the curing catalyst, without the addition ofsilicate, the recovery properties were especially low and creepresistance was poor. However, as illustrated in Example 1, the additionof silicate dramatically improved recovery properties and creepresistance. As illustrated by Comparative Example 2, when tincarboxylate (Neostann U-50) or the like was used as the curing catalystrather than organotin (U-220), good recovery properties and creepresistance were exhibited even without the addition of silicate,although as illustrated in Examples 2 to 4, even more superior recoveryproperties and creep resistance were exhibited with silicate addition.The Ethyl Silicate 40 and Methyl Silicate 51 used in Examples 3 and 4are condensates of respectively tetraethoxysilane andtetramethoxysilane, and exhibited especially excellent effects.

Synthesis Example 2

Using polyoxypropylene glycol having a molecular weight of about 2,000as an initiator, propylene oxide was polymerized in the presence of azinc hexacyanocobaltate glyme complex catalyst to obtain ahydroxyl-terminated polypropylene oxide having a number averagemolecular weight of about 14,500. This hydroxyl-terminated polypropyleneoxide was employed to obtain an allyl-terminated polypropylene oxideusing the same steps as those used in Synthesis Example 1. Thisallyl-terminated polypropylene oxide was, in the same manner as inSynthesis Example 1, reacted with trimethoxysilane to obtain apolyoxypropylene polymer (A-2) having on its terminals an average of 1.5trimethoxysilyl.

Synthesis Example 3

Using the same steps as those in Synthesis Example 1, theallyl-terminated polypropylene oxide obtained in Synthesis Example 2 wasreacted with triethoxysilane to obtain a polyoxypropylene polymer (A-3)having on its terminals an average of 1.5 triethoxysilyl groups.

Synthesis Example 4

Using the same steps as those of Synthesis Example 1, theallyl-terminated polypropylene oxide obtained in Synthesis Example 2 wasreacted with methyldimethoxysilane to obtain a polyoxypropylene polymer(A-4) having on its terminals an average of 1.5 methyldimethoxysilylgroups.

Examples 5 to 11 and Comparative Examples 3 to 5

Added together in accordance with the mixing formulation shown in Table2 were 100 parts by weight of the reactive silicon group-containingorganic polymer (A-2 to A-4) obtained in Synthesis Examples 2 to 4, 120parts by weight of surface-treated precipitated calcium carbonate(manufactured by Shiraishi Kogyo Co., Ltd. under the trade name ofHAKUENKA CCR), 20 parts by weight of titanium oxide (manufactured byIshihara Sangyo Kaisha, Ltd., under the trade name of Tipaque R-820), 12parts by weight of a plasticizer diisodecyl phthalate (manufactured byNew Japan Chemical Co., Ltd., under the trade name SANSOCIZER DIDP), 2parts by weight of a thixotropy imparting agent (manufactured byKusumoto Chemicals, Ltd., under the trade name Disparlon 6500), 1 partby weight of a photostabilizer (manufactured by Sankyo Co., Ltd. underthe trade name of Sanol LS-770), 1 part by weight of an ultravioletabsorber (manufactured by Ciba Specialty Chemicals, under the trade nameof TINUVIN 327), 1 part by weight of an antioxidant (manufactured byOuchi Shinko Chemical Industrial Co., Ltd., under the trade name NocracSP), 2 parts by weight of the dehydrating agent vinyltrimethoxysilane(manufactured by Nippon Unicar Co., Ltd. under the trade name of A-171),3 parts by weight of an adhesion-imparting agentN-(β-aminoethyl)-γ-aminopropyltrimethoxysilane (manufactured by NipponUnicar Co., Ltd. under the trade name of A-1120), the amount shown inTable 2 of a silicate (manufactured by Colcoat Co., Ltd., under thetrade name Methyl Silicate 51), the amount shown in Table 2 of thecuring catalyst of component (D) (dibutyltin bisacetylacetonate,manufactured by Nitto Kasei Co., Ltd. under the trade name of U-220);dibutyltin dilaurate, manufactured by Sankyo Co., Ltd. under the tradename of STANN BL), or the curing catalyst of component (C) (tinneodecanoate (divalent), manufactured by Nitto Kasei Co., Ltd. under thetrade name of U-50) and an amine (laurylamine, manufactured by Wako PureChemical Industries, Ltd.). The resultant mixture was kneaded underdehydrating conditions in a state in which the mixture was essentiallyfree from water, then sealed into a moisture-proof container to obtain aone-part curable composition.

Each of the compositions of Table 2 was subjected to a tensile test inthe same manner as that described above for measuring the M50: 50%tensile modulus (MPa), Tb: tensile strength at break (MPa) and Eb: theelongation at break (%). Results are shown in Table 2.

Each of the compositions shown in Table 2 was measured for recoveryratio in the same manner as that described above. However, in thepresent test, the 100% elongation state was fixed at 23° C. for 24hours, released at 23° C., whereby the recovery ratio was determinedfrom the ratio that the token line had recovered after 1 hour. Resultsare shown in Table 2.

(Creep Test Employing a Shear Sample)

Using each of the compositions of Table 2, shear samples were preparedhaving an area of 20 mm×25 mm and a thickness of 1 mm. These sampleswere aged at 23° C. for 3 days and 50° C. for 4 days, and were then putinto a 60° C. oven. A 0.1 MPa load was placed on each sample, wherebythe displacement difference between immediately after the load wasplaced and 140 hours after the load was placed was measured. Adisplacement difference of less than 0.4 mm was evaluated as “G” and adisplacement difference of 0.4 mm or more was evaluated as “P”. Resultsare shown in Table 2.

A comparison of Examples 5 to 9 with Comparative Examples 3 to 5 fromTable 2 shows that the use of an organic polymer (A-2 or A-3) in whichthe terminal reactive silicon group is a trialkoxysilyl groupdramatically improves recovery properties and creep resistance.Moreover, Example 10, in which a silicate was added, and Example 11, inwhich tin carboxylate (Neostann U-50) was used as the curing catalyst,exhibited an even more superior recovery ratio.

Synthesis Example 5

Using the same steps as those of Synthesis Example 1, theallyl-terminated polypropylene oxide obtained in Synthesis Example 1 wasreacted with methyl dimethoxy silane to obtain a polyoxypropylenepolymer (A-5) having on its terminals an average of 2methyldimethoxysilyl groups.

Synthesis Example 6

Using polyoxypropylene triol having a molecular weight of about 3,000 asan initiator, propylene oxide was polymerized in the presence of a zinchexacyanocobaltate glyme complex catalyst to obtain ahydroxyl-terminated polypropylene oxide having a number averagemolecular weight of about 26,000. This hydroxyl-terminated polypropyleneoxide was employed to obtain a metallyl-terminated polypropylene oxideusing the same steps as those used in Synthesis Example 1, except thatmetallyl chloride was used in place of allyl chloride. Using 0.5 partsby weight of isopropanol solution of platinum vinyldisiloxane complex of3 wt. % in terms of platinum as a catalyst, sulfur was mixed in relationto 100 parts by weight of the metallyl-terminated polypropylene oxide,in a sulfur 1 eq/Pt 1 eq ratio, under a nitrogen atmosphere containing 6vol % oxygen. The resultant mixture was reacted with 3.2 parts by weightof methyl dimethoxysilane at 90° C. for 5 hours, to thereby obtain apolyoxypropylene polymer (A-6) having an average of 2.8methyldimethoxysilyl groups on its terminals. TABLE 2 Structure ofreactive Example Comparative Example Composition (parts by weight)silicon group 5 6 7 8 9 10 11 3 4 5 Organic Component A-2Trimethoxysilyl group 100 100 polymer (A1) A-3 Triethoxysilyl group 100100 100 100 100 A-4 Methyldimethoxysilyl 100 100 100 group FillerHAKUENKA CCR 120 120 120 120 120 120 120 120 120 120 Tipaque R-820 20 2020 20 20 20 20 20 20 20 Plasticizer SANSOCIZER-DIDP 12 12 12 12 12 12 1212 12 12 Thixotropy imparting Disparlon #6500 2 2 2 2 2 2 2 2 2 2 agentPhotostabilizer Sanol LS-770 1 1 1 1 1 1 1 1 1 1 Ultraviolet AbsorberTINUVIN 327 1 1 1 1 1 1 1 1 1 1 Antioxidant Nocrac SP 1 1 1 1 1 1 1 1 11 Dehydrating Agent A-171 2 2 2 2 2 2 2 2 2 2 Adhesion-imparting A-11203 3 3 3 3 3 3 3 3 3 agent Silicate Component Methyl Silicate 51 2 (B)Curing Component Neostann U-220 0.2 0.2 2 2 0.2 2 Catalyst (D) Stann BL0.3 3 3 Component Neostann U-50 3.4 (C) Amine Laurylamine 0.75 RecoveryRatio (%) 93 93 93 93 94 96 96 67 47 64 Creep (shear) “G” “G” “G” “G”“G” “G” “G” “P” “P” “P” Cured M50 (MPa) 0.94 0.95 1.13 0.92 0.92 1.150.94 1.01 0.85 0.82 Article Tb (MPa) 2.24 2.20 2.61 2.35 2.08 2.20 2.182.83 2.84 2.70 Proper- Eb (%) 193 196 184 208 208 167 216 269 340 370ties

Examples 12 to 14 and Comparative Example 6

Added together in accordance with the mixing formulation shown in Table3 were 100 parts by weight of the reactive silicon group-containingorganic polymer (A-1 or A-4 to A-6) obtained in Synthesis Examples 1 and4 to 6, 120 parts by weight of surface-treated precipitated calciumcarbonate (manufactured by Shiraishi Kogyo Co., Ltd. under the tradename of HAKUENKA CCR), 20 parts by weight of titanium oxide(manufactured by Ishihara Sangyo Kaisha, Ltd., under the trade name ofTipaque R-820), 55 parts by weight of a plasticizer diisodecyl phthalate(manufactured by New Japan Chemical Co., Ltd., under the trade nameSANSOCIZER DIDP), 2 parts by weight of a thixotropy imparting agent(manufactured by Kusumoto Chemicals, Ltd., under the trade nameDisparlon 6500), 1 part by weight of a photostabilizer (manufactured bySankyo Co., Ltd. under the trade name of Sanol LS-770), 1 part by weightof an ultraviolet absorber (manufactured by Ciba Specialty Chemicals,under the trade name of TINUVIN 327), 1 part by weight of an antioxidant(manufactured by Ouchi Shinko Chemical Industrial Co., Ltd., under thetrade name Nocrac SP), 2 parts by weight of a dehydrating agentvinyltrimethoxysilane (manufactured by Nippon Unicar Co., Ltd. under thetrade name of A-171), 3 parts by weight of an adhesion-imparting agentN-(β-aminoethyl)-γ-aminopropyltrimethoxysilane (manufactured by NipponUnicar Co., Ltd. under the trade name of A-1120), and as the curingcatalyst, 3.4 parts by weight of tin carboxylate (tin neodecanoate(divalent), manufactured by Nitto Kasei Co., Ltd. under the trade nameof U-50), 1.2 parts by weight of a carboxylic acid (neodecanoic acid,manufactured by Japan Epoxy Resins Co., Ltd. under the trade name ofVersatic 10) and 0.75 parts by weight of an amine (laurylamine,manufactured by Wako Pure Chemical Industries, Ltd.). The resultantmixture was kneaded under dehydrating conditions in a state in which themixture was essentially free from water, then sealed into amoisture-proof container to obtain a one-part curable composition.

Each of the compositions of Table 3 was subjected to a tensile test inthe same manner as that described above for measuring the M50:50%tensile modulus (MPa), Tb: tensile strength at break (MPa) and Eb: theelongation at break (%). Results are shown in Table 3.

Each of the compositions of Table 3 was measured for recovery ratio inthe same manner as that described above. However, in the present test,the 100% elongation state was fixed at 60° C. for 24 hours, released at23° C., whereby the recovery ratio was determined from the ratio thatthe token line had recovered after 1 hour. Results are shown in Table 3.

Each of the compositions shown in Table 3 was subjected to a creep test,in the same manner as that described above for Examples 1 to 4, by usinga dumbbell specimen for measuring the displacement difference of thetoken line interval distances between immediately after a load wasplaced and 200 hours after the load had been placed. Results are shownin Table 3. TABLE 3 Number of Reactive Silicon Comparative Groups PerExample Example Composition (parts by weight) Molecule 12 13 14 6Organic Component (A2) A-5 2.0 100 Polymer A-1 2.3 100 A-6 2.8 100 A-41.5 100 Filler HAKUENKA CCR 120 120 120 120 Tipaque R-820 20 20 20 20Plasticizer SANSOCIZER DIDP 55 55 55 55 Thixotropy Imparting AgentDisparlon #6500 2 2 2 2 Photostabilizer Sanol LS-770 1 1 1 1 UltravioletAbsorber TINUVIN 327 1 1 1 1 Antioxidant Nocrac SP 1 1 1 1 DehydratingAgent A-171 2 2 2 2 Adhesion-imparting agent A-1120 3 3 3 3 Curing TinNeostann U-50 3.4 3.4 3.4 3.4 Catalyst Carboxylate Carboxylic Versatic10 1.2 1.2 1.2 1.2 Acid Amine laurylamine 0.75 0.75 0.75 0.75 RecoveryRatio (%) 78 81 86 73 Creep (mm) 2.5 2.2 1.3 3.2 Cured M50 (MPa) 0.350.43 0.68 0.38 Article Tb (MPa) 2.39 2.30 1.87 2.02 Properties Eb (%)601 483 273 502

A comparison of Examples 12 to 14 with Comparative Example 6 of Table 3shows that organic polymers (A-1, A-5 and A-6) which have a high numberof reactive silicon groups per molecule possess excellent recoveryproperties and creep resistance.

Synthesis Example 7

Using polyoxypropylene glycol having a molecular weight of about 2,000as an initiator, propylene oxide was polymerized in the presence of azinc hexacyanocobaltate glyme complex catalyst to obtain ahydroxyl-terminated polypropylene oxide having a number averagemolecular weight of about 28,500. This hydroxyl-terminated polypropyleneoxide was employed to obtain a metallyl-terminated polypropylene oxideusing the same steps as those used in Synthesis Example 6. Using thesame steps as those of Synthesis Example 6, the metallyl-terminatedpolypropylene oxide was reacted with methyldimethoxysilane to obtain apolyoxypropylene polymer (A-7) having on its terminals an average of 1.9methyldimethoxysilyl groups.

Synthesis Example 8

Using the same steps as those of Synthesis Example 6, themetallyl-terminated polypropylene oxide obtained in Synthesis Example 7was reacted with methyldimethoxysilane to obtain a polyoxypropylenepolymer (A-8) having on its terminals an average of 1.5methyldimethoxysilyl.

Synthesis Example 9

Using polyoxypropylene glycol having a molecular weight of about 2,000as an initiator, propyleneoxide was polymerized in the presence of azinc hexacyanocobaltate glyme complex catalyst to obtain ahydroxyl-terminated polypropylene oxide having a number averagemolecular weight of about 28,500. This hydroxyl-terminated polypropyleneoxide was employed to obtain an allyl-terminated polypropylene oxideusing the same steps as those used in Synthesis Example 1. Using thesame steps as those of Synthesis Example 1, the allyl-terminatedpolypropylene oxide was reacted with methyldimethoxysilane to obtain apolyoxypropylene polymer (A-9) having on its terminals an average of 1.5methyldimethoxysilyl groups.

Examples 15 and 16 and Comparative Examples 7 and 8

Added together in accordance with the mixing formulation shown in Table4 were 100 parts by weight of the reactive silicon group-containingorganic polymer (A-4 or A-7 to A-9) obtained in Synthesis Examples 4 and7 to 9, 120 parts by weight of surface-treated precipitated calciumcarbonate (manufactured by Shiraishi Kogyo Co., Ltd. under the tradename of HAKUENKA CCR), 20 parts by weight of titanium oxide(manufactured by Ishihara Sangyo Kaisha, Ltd., under the trade name ofTipaque R-820), 55 parts by weight of a plasticizer diisodecyl phthalate(manufactured by New Japan Chemical Co., Ltd., under the trade nameSANSOCIZER DIDP), 2 parts by weight of a thixotropy imparting agent(manufactured by Kusumoto Chemicals, Ltd., under the trade nameDisparlon 6500), 1 part by weight of a photostabilizer (manufactured bySankyo Co., Ltd. under the trade name of Sanol LS-770), 1 part by weightof an ultraviolet absorber (manufactured by Ciba Specialty Chemicals,under the trade name of TINUVIN 327), 1 part by weight of an antioxidant(manufactured by Ouchi Shinko Chemical Industrial Co., Ltd., under thetrade name Nocrac SP), 2 parts by weight of the dehydrating agentvinyltrimethoxysilane (manufactured by Nippon Unicar Co., Ltd. under thetrade name of A-171), 3 parts by weight of an adhesion-imparting agentN-(β-aminoethyl)-γ-aminopropyltrimethoxysilane (manufactured by NipponUnicar Co., Ltd. under the trade name of A-1120), and 2 parts by weightof the curing catalyst dibutyltin bisacetylacetonate (manufactured byNitto Kasei Co., Ltd. under the trade name of Neostann U-220). Theresultant mixture was kneaded under dehydrating conditions in a state inwhich the mixture was essentially free from water, then sealed into amoisture-proof container to obtain a one-part curable composition.

Each of the compositions of Table 4 was subjected to a tensile test inthe same manner as that described above for measuring the M50:50%tensile modulus (MPa), Tb: tensile strength at break (MPa) and Eb: theelongation at break (%). Results are shown in Table 4.

Each of the compositions of Table 4 was measured for recovery ratio inthe same manner as that described above. However, in the present test,the 100% elongation state was fixed at 23° C. for 24 hours, released at23° C., whereby the recovery ratio was determined from the ratio thatthe token line had recovered after 24 hour. Results are shown in Table4.

Each of the compositions of Table 4 was subjected to a creep test usinga dumbbell specimen in the same manner as that described above forExamples 1 to 4 for measuring the displacement difference of the tokenline interval distances between immediately after the load was placedand 45 hours after the load was placed. Results are shown in Table 4.

A comparison of Examples 15 and 16 with Comparative Examples 7 and 8 ofTable 4 shows that organic polymers (A-7 and A-8), in which a reactivesilicon group is introduced into a metallyl-terminated polymer, possessexcellent recovery properties and creep resistance. TABLE 4 Structure ofterminal Number of group before reactive silicon Comparative introducingreactive groups per Example Example Composition (parts by weight)silicon group molecule 15 16 7 8 Organic Component (A3) A-7 Methallylgroup 1.9 100 polymer A-8 Methallyl group 1.5 100 A-9 Allyl group 1.5100 A-4 Allyl group 1.5 100 Filler HAKUENKA CCR 120 120 120 120 TipaqueR-820 20 20 20 20 Plasticizer SANSOCIZER-DIDP 55 55 55 55 Thixotropyimparting agent Disparlon #6500 2 2 2 2 Photostabilizer Sanol LS-770 1 11 1 Ultraviolet Absorber TINUVIN 327 1 1 1 1 Antioxidant Nocrac SP 1 1 11 Dehydrating Agent A-171 2 2 2 2 Adhesion-imparting agent A-1120 3 3 33 Curing Catalyst Neostann U-220 2 2 2 2 Recovery Ratio (%) 86 84 74 75Creep (mm) 15 22 44 41 Cured Article M50 (MPa) 0.41 0.21 0.19 0.39Properties Tb (MPa) 2.71 3.02 2.60 1.90 Eb (%) 652 1019 1018 403

Synthesis Example 10

Using the same steps as those of Synthesis Example 1, theallyl-terminated polypropylene oxide obtained in Synthesis Example 1 wasreacted with triethoxysilane to obtain a polyoxypropylene polymer (A-10)having on its terminals an average of 2.3 triethoxysilyl groups.

Examples 17 and 18 and Comparative Example 9

Added together in accordance with the mixing formulation shown in Table5 were 100 parts by weight of the reactive silicon group-containingorganic polymer (A-1 or A-10) obtained in Synthesis Examples 1 and 10,120 parts by weight of surface-treated precipitated calcium carbonate(manufactured by Solvay S.A., under the trade name of Winnofil SPM), 20parts by weight of titanium oxide (manufactured by Kerr-McGeeCorporation, under the trade name of RFK-2), 50 parts by weight of aplasticizer diisoundecyl phthalate (manufactured by Exxon Mobil ChemicalCorporation, under the trade name JAYFLEX DIUP), 5 parts by weight of athixotropy imparting agent (manufactured by Cray Valley, under the tradename Crayvallac super), 1 part by weight of a photostabilizer(manufactured by Sankyo Co., Ltd. under the trade name of Sanol LS-770),1 part by weight of an ultraviolet absorber (manufactured by CibaSpecialty Chemicals, under the trade name of TINUVIN 327), 1 part byweight of an antioxidant (manufactured by Ouchi Shinko ChemicalIndustrial Co., Ltd., under the trade name Nocrac SP), 2 parts by weightof vinyltrimethoxysilane as a dehydrating agent (manufactured by NipponUnicar Co., Ltd. under the trade name of A-171), 3 parts by weight ofcomponent (G) γ-aminopropyltriethoxysilane (manufactured by NipponUnicar Co., Ltd. under the trade name of A-1100) orN-(β-aminoethyl)-γ-aminopropyltrimethoxysilane (manufactured by NipponUnicar Co., Ltd. under the trade name of A-1120) as a adhesion-impartingagent, and 2 parts by weight of the curing catalystdibutyltinbisacetylacetonate (manufactured by Nitto Kasei Co., Ltd.under the trade name of Neostann U-220). The resultant mixture waskneaded under dehydrating conditions in a state in which the mixture wasessentially free from water, then sealed into a moisture-proof containerto obtain a one-part curable composition.

Each of the compositions of Table 5 was measured for recovery ratio inthe same manner as that described above. However, in the present test,the 100% elongation state was fixed at 60° C. for 24 hours, released at23° C., whereby the recovery ratio was determined from the ratio thatthe token line had recovered after 1 hour. Results are shown in Table 5.

Using each of the compositions shown in Table 5, shear samples wereprepared in the same manner as that of Examples 5 to 11 and subjected toa creep test. The displacement difference of the token line intervaldistances between immediately after the load was placed and 140 hoursafter the load was placed was measured. The evaluation standards wereset at a displacement difference of less than 0.4 mm being evaluated asa “G” and a displacement difference of 0.4 mm or more as a “P”. Resultsare shown in Table 5. TABLE 5 Structure of the Comparative ReactiveExample Example Composition (parts by weight) Silicon Group 17 18 9Organic Component (A4) A-10 Triethoxysilyl 100 100 Polymer Group A-1Methyldimethoxysilyl 100 Group Filler Winnofil SPM 120 120 120 RFK-2 2020 20 Plasticizer JAYFLEX DIUP 50 50 50 Thixotropy Imparting AgentCrayvallac super 5 5 5 Photostabilizer Sanol LS-770 1 1 1 UltravioletAbsorber TINUVIN 327 1 1 1 Antioxidant Nocrac SP 1 1 1 Dehydrating AgentA-171 2 2 2 Adhesion- Component (G) A-1100 Triethoxysilyl 3 impartingGroup agent A-1120 Trimethoxysilyl 3 3 Group Curing Catalyst NeostannU-220 2 2 2 Recovery Ratio (%) 87 85 25 Creep (shear) “G” “G” “P” SkinFormation Pre-storage (min) 20 15 15 Time 50° C. × 7 days (min) 20 5 15Post-storage(Curability of the Curable Composition)

Each of the compositions shown in Table 5 was thinly extended to athickness of about 3 mm. The time taken until a skin covered the surface(skin formation time) under the conditions of 23° C. and a humidity of50% RH was measured. A shorter skin formation time indicated superiorcurability. Results are shown in Table 5.

As illustrated in Example 17 of Table 5, using a (A2) component polymerhaving a triethoxysilyl group on its terminal as the organic polymer incombination with an aminosilane as (G) component having thetriethoxysilyl group as the adhesion-imparting agent, provides forexcellent recovery properties and creep resistance as well as goodstorage stability in which there was little variation in skin formationtime before and after storage.

Example 19 and Comparative Examples 10 and 11

Added together in accordance with the mixing formulation shown in Table6 were 100 parts by weight of the reactive silicon group-containingorganic polymer (A-2) obtained in Synthesis Example 2, 30 parts byweight of a plasticizer diisodecyl phthalate (manufactured by New JapanChemical Co., Ltd., under the trade name SANSOCIZER DIDP), 2 parts byweight of tetraethoxysilane (manufactured by Colcoat Co., Ltd., underthe trade name Ethyl Silicate 28) as the dehydrating agent, 3 parts byweight of the component (H)N-(β-aminoethyl)-γ-aminopropyltrimethoxysilane (manufactured by NipponUnicar Co., Ltd. under the trade name of A-1120) orN-(β-aminoethyl)-γ-aminopropyltriethoxysilane (manufactured by Shin-EtsuChemical Co., Ltd. under the trade name of KBE-603) as aadhesion-imparting agent, and 2 parts by weight of the curing catalystdibutyltin bisacetylacetonate (manufactured by Nitto Kasei Co., Ltd.under the trade name of Neostann U-220). The resultant mixture wassealed into a glass container that had been purged with nitrogen toobtain a one-part curable composition. In Comparative Example 10, theskin formation time test was carried out under conditions of 23° C.temperature and 50% RH humidity without aging the obtained one-partcurable composition. In Example 19 and Comparative Example 11, an esterexchange reaction was promoted among the reactive silicon groups byaging the obtained one-part curable composition at 50° C. for 7 days,whereafter the skin formation time test was carried out under conditionsof 23° C. temperature and 50% RH humidity. Results are shown in Table 6.TABLE 6 Composition Structure of the Comparative (parts by ReactiveSilicon Example Example weight) Group 19 10 11 Organic Component (A4)A-2 Triethoxysilyl 100 100 100 Polymer Group Plasticizer SANSOCIZER DIDP30 30 30 Dehydrating Agent Ethyl Silicate 28 2 2 2 Adhesion-imparatingComponent (H) A-1120 Trimethoxysilyl 3 3 agent Group KBE-603Triethoxysilyl 3 Group Curing Catalyst Neostann U-220 2 2 2 50° C. × 7days Aging yes no yes Skin Formation Time (min) 3 13 12

As illustrated in Example 19 of Table 6, using a (A2) component polymerhaving a triethoxysilyl group on its terminal as the organic polymer incombination with an aminosilane as (H) component having the methoxysilylgroup as the adhesion-imparting agent, enables a dramatic improvement inthe curability of the organic polymer, if an ester exchange reactionthrough aging is promoted.

Examples 20 and 21

Added together were 100 parts by weight of the reactive silicongroup-containing organic polymer (A-10) obtained in Synthesis Example10, 120 parts by weight of surface-treated precipitated calciumcarbonate (manufactured by Shiraishi Kogyo Co., Ltd. under the tradename of HAKUENKA CCR), 20 parts by weight of titanium oxide(manufactured by Ishihara Sangyo Kaisha, Ltd., under the trade name ofTipaque R-820), 55 parts by weight of a plasticizer diisodecyl phthalate(manufactured by New Japan Chemical Co., Ltd., under the trade nameSANSOCIZER DIDP), 2 parts by weight of a thixotropy imparting agent(manufactured by Kusumoto Chemicals, Ltd., under the trade nameDisparlon 6500), 1 part by weight of a photostabilizer (manufactured bySankyo Co., Ltd. under the trade name of Sanol LS-770), 1 part by weightof an ultraviolet absorber (manufactured by Ciba Specialty Chemicals,under the trade name of TINUVIN 327), 1 part by weight of an antioxidant(manufactured by Ouchi Shinko Chemical Industrial Co., Ltd., under thetrade name Nocrac SP), 2 parts by weight of the dehydrating agentvinyltrimethoxysilane (manufactured by Nippon Unicar Co., Ltd. under thetrade name of A-171), 3 parts by weight of an adhesion-imparting agentN-(β-aminoethyl)-γ-aminopropyltrimethoxysilane (manufactured by NipponUnicar Co., Ltd. under the trade name of A-1120), and the respectivekinds of curing catalyst which shall be described below. The resultantmixture was kneaded under dehydrating conditions in a state in which themixture was essentially free from water, then sealed into amoisture-proof container to obtain a one-part curable composition. Asthe curing catalyst, Example 20 used a mixture to which 6 parts byweight of neodecanoic acid (manufactured by Japan Epoxy Resins Co., Ltd.under the trade name of Versatic 10), which is the non-tin catalyst ofcomponent (E), and 0.75 parts by weight of an amine (laurylamine,manufactured by Wako Pure Chemical Industries, Ltd.) had been added,while Example 21 used a mixture to which 2 parts by weight of dibutyltinbisacetylacetonate (manufactured by Nitto Kasei Co., Ltd. under thetrade name of Neostann U-220) had been added.

Each of these compositions was measured for recovery ratio in the samemanner as that described above. However, in the present test, the 100%elongation state was fixed at 80° C. for 24 hours, released at 23° C.,whereby the recovery ratio was determined from the ratio that the tokenline had recovered after 1 hour. The results showed that the recoveryratios of Example 20 and Example 21 were both high at respectively 86%and 80%, although the combination with the non-tin catalyst of Example20 showed an especially high recovery ratio.

Synthesis Example 11

Using polyoxypropylene glycol having a molecular weight of about 2,000as an initiator, propyleneoxide was polymerized in the presence of azinc hexacyanocobaltate glyme complex catalyst to obtain ahydroxyl-terminated polypropylene oxide having a number averagemolecular weight of about 25,500. This hydroxyl-terminated polypropyleneoxide was employed to obtain an allyl-terminated polypropylene oxideusing the same steps as those used in Synthesis Example 1. Thisallyl-terminated polypropylene oxide was, in the same manner as inSynthesis Example 1, reacted with triethoxysilane to obtain apolyoxypropylene polymer (A-11) having on its terminals an average of1.5 triethoxysilyl groups.

Synthesis Example 12

The allyl-terminated polypropylene oxide obtained in Synthesis Example11 was, in the same manner as in Synthesis Example 1, reacted withmethyldimethoxysilane to obtain a polyoxypropylene polymer (A-12) havingon its terminals an average of 1.5 methyldimethoxysilyl groups.

Examples 22 and 23 and Comparative Examples 12 and 13

Weighed out in accordance with the mixing formulation shown in Table 7,and thoroughly kneaded using a paint roller with 3 rolls to form a mainingredient, were 95 parts by weight of the reactive silicongroup-containing organic polymer (A-11 or A-12) obtained in SynthesisExamples 11 and 12, 60 parts by weight of surface-treated precipitatedcalcium carbonate (manufactured by Shiraishi Kogyo Co., Ltd. under thetrade name of HAKUENKA CCR), 60 parts by weight of surface-treatedprecipitated calcium carbonate (manufactured by Shiraishi Kogyo Co.,Ltd. under the trade name of Viscolite R), 20 parts by weight of groundcalcium carbonate (manufactured by Shiraishi Calcium Co., Ltd. under thetrade name of Whiton SB), 40 parts by weight of a plasticizerdi-2-ethylhexyl phthalate (manufactured by New Japan Chemical Co., Ltd.,under the trade name SANSOCIZER DOP), 20 parts by weight of anepoxy-type plasticizer (manufactured by New Japan Chemical Co., Ltd.,under the trade name SANSOCIZER EP-S), 3 parts by weight of a thixotropyimparting agent (manufactured by Kusumoto Chemicals, Ltd., under thetrade name Disparlon 305), 3 parts by weight of a photocurable resin(manufactured by Toagosei Co., Ltd. under the trade name of ARONIXM-309), 1 part by weight of a photostabilizer (manufactured by SankyoCo., Ltd. under the trade name of Sanol LS-770), 1 part by weight of anultraviolet absorber (manufactured by Ciba Specialty Chemicals, underthe trade name of TINUVIN 327), 1 part by weight of an antioxidant(manufactured by Ciba Specialty Chemicals, under the trade name Irganox1010), and 0 parts or 20 parts of the component (F) microballoons(manufactured by Fuji Silysia Chemical Ltd., under the trade name FujiBalloon H-40). In Example 22, a mixture was used which employed (A-11)as the organic polymer and contained 20 parts of the microballoons,while in Example 23 a mixture was used which employed (A-11) as theorganic polymer and contained 0 parts of the microballoons. InComparative Example 12, a mixture was used which employed (A-12) as theorganic polymer and contained 20 parts of the microballoons, while inComparative Example 13 a mixture was used which employed (A-12) as theorganic polymer and contained 0 parts of the microballoons.

A curing agent consisting of 3 parts by weight of tin 2-ethylhexanoate(divalent) (manufactured by Nitto Kasei Co., Ltd. under the trade nameof U-28) and 0.75 parts by weight of an amine (laurylamine, manufacturedby Wako Pure Chemical Industries, Ltd.) was mixed with theabove-described main ingredient to form a uniform mixture for evaluatingworkability (thread-pulling properties) and the compression recoveryratio.

(Compression Recovery Ratio)

H-shaped specimens as defined in JIS A 5758 were prepared using each ofthe compositions of Table 7, and subjected to aging at 23° C. for 7 daysand 50° C. for 7 days. The specimens were immersed in 50° C. warm waterfor 24 hours, then allowed to stand under normal conditions of 23° C.for 24 hours. The H-shaped specimens were then compressed by 30%, andfixed at 90° C. for 7 days. The specimens were released at 23° C., andthe recovery ratio was measured after 24 hours. A greater recovery ratioindicated superior recovery properties. Results are shown in Table 7.TABLE 7 Composition Comparative (parts by Reactive Silicon ExampleExample weight) Group Structure 22 23 12 13 Organic Component (A4) A-11Triethoxysilyl 95 95 Polymer Group A-12 Methyldimethoxysilyl 95 95 GroupFiller HAKUENKA CCR 60 60 60 60 Viscolite R 60 60 60 60 Whiton SB 20 2020 20 Plasticizer SANSOCIZER DOP 40 40 40 40 SANSOCIZER EP-S 20 20 20 20Thixotropy Imparting Agent Disparlon #309 3 3 3 3 Photocurable ResinARONIX M-309 3 3 3 3 Photostabilizer Sanol LS-770 1 1 1 1 UltravioletAbsorber TINUVIN 327 1 1 1 1 Antioxidant Irganox 1010 1 1 1 1Microballoons Component (F) Fuji Balloon H-40 20 0 20 0 Curing TinNeostann U-28 3 3 3 3 Catalyst Carboxylate Amine Laurylamine 0.75 0.750.75 0.75 Workability “G” “M” “G” “M” Compression Recovery Ratio (%) 6459 39 36

The composition of Example 22 had superior workability than that ofExample 23, and a superior recovery ratio to those of ComparativeExamples 12 and 13.

Examples 24 and 25 and Comparative Examples 14 to 16

Weighed out in accordance with the mixing formulation shown in Table 8,and thoroughly kneaded using a paint roller with 3 rolls to form a mainingredient, were 60 parts by weight of a surface-treated precipitatedcalcium carbonate (manufactured by Shiraishi Kogyo Co., Ltd. under thetrade name of HAKUENKA CCR), 60 parts by weight of a surface-treatedprecipitated calcium carbonate (manufactured by Shiraishi Kogyo Co.,Ltd. under the trade name of Viscolite R), 20 parts by weight of groundcalcium carbonate (manufactured by Shiraishi Calcium Co., Ltd. under thetrade name of Whiton SB), 40 parts by weight of a plasticizerdi-2-ethylhexyl phthalate (manufactured by New Japan Chemical Co., Ltd.,under the trade name SANSOCIZER DOP), 20 parts by weight of anepoxy-type plasticizer (manufactured by New Japan Chemical Co., Ltd.,under the trade name SANSOCIZER EP-S), 3 parts by weight of a thixotropyimparting agent (manufactured by Kusumoto Chemicals, Ltd., under thetrade name Disparlon 305), 3 parts by weight of a photocurable resin(manufactured by Toagosei Co., Ltd. under the trade name of ARONIXM-309), 1 part by weight of a photostabilizer (manufactured by SankyoCo., Ltd. under the trade name of Sanol LS-770), 1 part by weight of anultraviolet absorber (manufactured by Ciba Specialty Chemicals, underthe trade name of TINUVIN 327), and 1 part by weight of an antioxidant(manufactured by Specialty Chemicals, under the trade name Irganox1010). The amount defined in Table 8 of the reactive silicongroup-containing organic polymer (A-10) obtained in Synthesis Example 10or the reactive silicon group-containing organic polymer (A-1) obtainedin Synthesis Example 1 was added to this main ingredient. In Example 24,70 parts of (A-10) had been added as the organic polymer, while inExample 25 50 parts of (A-10) had been added as the organic polymer. InComparative Example 14, 95 parts of (A-1) had been added as the organicpolymer, while in Comparative Example 15 70 parts of (A-1) had beenadded as the organic polymer, and in Comparative Example 16 50 parts of(A-1) had been added as the organic polymer. Mixed into this mainingredient was a curing agent consisting of 3 parts by weight of tin2-ethylhexanoate (divalent) (manufactured by Nitto Kasei Co., Ltd. underthe trade name of U-28) and 0.75 parts by weight of an amine(laurylamine, manufactured by Wako Pure Chemical Industries, Ltd.).Dumbbell-type cured articles were prepared in the same manner as thatdescribed above for evaluation of the recovery properties. However, inthe present test, the 100% elongation state was fixed at 90° C. for 24hours, released at 23° C., whereby the recovery ratio was determinedfrom the ratio that the token line had recovered after hour. Results areshown in Table 8. TABLE 8 Comparative Structure of reactive ExampleExample Composition (parts by weight) silicon group 24 25 14 15 16Organic polymer Component (A4) A-10 Triethoxysilyl group 70 50 A-1Methyldimethoxysilyl group 95 70 50 Filler HAKUENKA CCR 60 60 60 60 60Viscolite R 60 60 60 60 60 Whiton SB 20 20 20 20 20 PlasticizerSANSOCIZER-DOP 40 40 40 40 40 SANSOCIZER-E-PS 20 20 20 20 20 Thixotropyimparting agent Disparlon #309 3 3 3 3 3 Photocurable resin ARONIX M-3093 3 3 3 3 Photostabilizer Sanol LS-770 1 1 1 1 1 Ultraviolet AbsorberTINUVIN 327 1 1 1 1 1 Antioxidant Irganox 1010 1 1 1 1 1 Curing catalystTin carboxylate Neostann U-28 3 3 3 3 3 Amine Laurylamine 0.75 0.75 0.750.75 0.75 Wt % of organic polymer in (wt %) 25 19 31 25 19 thecomposition Recovery Ratio (%) 91 88 77 69 66

The compounds of Examples 24 and 25, while suppressing the weight % ofthe organic polymer, showed a higher recovery ratio than that ofComparative Example 14, which had a high weight % of organic polymer.

Examples 26 and 27

Weighed out and thoroughly kneaded using a paint roller with 3 rolls toform a main ingredient were 95 parts by weight of the reactive silicongroup-containing organic polymer (A-10) obtained in Synthesis Example10, 60 parts by weight of surface-treated precipitated calcium carbonate(manufactured by Shiraishi Kogyo Co., Ltd. under the trade name ofHAKUENKA CCR), 60 parts by weight of surface-treated precipitatedcalcium carbonate (manufactured by Shiraishi Kogyo Co., Ltd. under thetrade name of Viscolite R), 20 parts by weight of ground calciumcarbonate (manufactured by Shiraishi Calcium Co., Ltd. under the tradename of Whiton SB), 40 parts by weight of a plasticizer di-2-ethylhexylphthalate (manufactured by New Japan Chemical Co., Ltd., under the tradename SANSOCIZER DOP), 20 parts by weight of an epoxy-type plasticizer(manufactured by New Japan Chemical Co., Ltd., under the trade nameSANSOCIZER EP-S), 3 parts by weight of a thixotropy imparting agent(manufactured by Kusumoto Chemicals, Ltd., under the trade nameDisparlon 305), 3 parts by weight of a photocurable resin (manufacturedby Toagosei Co., Ltd. under the trade name of ARONIX M-309), 1 part byweight of a photostabilizer (manufactured by Sankyo Co., Ltd. under thetrade name of Sanol LS-770), 1 part by weight of an ultraviolet absorber(manufactured by Ciba Specialty Chemicals, under the trade name ofTINUVIN 327), 1 part by weight of an antioxidant (manufactured by CibaSpecialty Chemicals, under the trade name Irganox 1010), and 0 parts or5 parts of an epoxy resin (manufactured by Japan Epoxy Resins Co., Ltd.,under the trade name of Epikote 828). The mixture which employed 5 partsof the epoxy resin was used for Example 26, while the mixture whichemployed 0 parts by weight of the epoxy resin was used for Example 27.Mixed into this main ingredient was a curing agent consisting of 3 partsby weight of tin 2-ethylhexanoate (divalent) (manufactured by NittoKasei Co., Ltd. under the trade name of U-28) and 0.75 parts by weightof an amine (laurylamine, manufactured by Wako Pure Chemical Industries,Ltd.). H-shaped cured articles were prepared in the same manner asdescribed above for measurement of the compression recovery ratio.

The compounds of Examples 26 and 27 both showed a high compressionrecovery ratio, although that of Example 26 in particular showed a highrecovery ratio from the combination with the epoxy resin.

Examples 28 and 29

Weighed out and thoroughly kneaded using a paint roller with 3 rolls toform a main ingredient were 95 parts by weight of the reactive silicongroup-containing organic polymer (A-10) obtained in Synthesis Example10, 60 parts by weight of surface-treated precipitated calcium carbonate(manufactured by Shiraishi Kogyo Co., Ltd. under the trade name ofHAKUENKA CCR), 60 parts by weight of surface-treated precipitatedcalcium carbonate (manufactured by Shiraishi Kogyo Co., Ltd. under thetrade name of Viscolite R), 20 parts by weight of ground calciumcarbonate (manufactured by Shiraishi Calcium Co., Ltd. under the tradename of Whiton SB), 40 parts by weight of a plasticizer di-2-ethylhexylphthalate (manufactured by New Japan Chemical Co., Ltd., under the tradename SANSOCIZER DOP), 20 parts by weight of an epoxy-type plasticizer(manufactured by New Japan Chemical Co., Ltd., under the trade nameSANSOCIZER EP-S), 3 parts by weight of a thixotropy imparting agent(manufactured by Kusumoto Chemicals, Ltd., under the trade nameDisparlon 305), 3 parts by weight of a photocurable resin (manufacturedby Toagosei Co., Ltd. under the trade name of ARONIX M-309), 1 part byweight of a photostabilizer (manufactured by Sankyo Co., Ltd. under thetrade name of Sanol LS-770), 1 part by weight of an ultraviolet absorber(manufactured by Ciba Specialty Chemicals, under the trade name ofTINUVIN 327), and 1 part by weight of an antioxidant (manufactured byCiba Specialty Chemicals, under the trade name Irganox 1010).

For Example 28, a mixture of 3 parts by weight of tin 2-ethylhexanoate(divalent) (manufactured by Nitto Kasei Co., Ltd. under the trade nameof U-28), 0.75 parts by weight of an amine (laurylamine, manufactured byWako Pure Chemical Industries, Ltd.) and 0.1 parts by weight ofdibutyltin bisacetylacetonate (manufactured by Nitto Kasei Co., Ltd.under the trade name of Neostann U-220) was used as the curing agent,while for Example 29, a mixture of 3 parts by weight of tin2-ethylhexanoate (divalent) (manufactured by Nitto Kasei Co., Ltd. underthe trade name of U-28) and 0.75 parts by weight of an amine(laurylamine, manufactured by Wako Pure Chemical Industries, Ltd.) wasused as the curing agent. The main ingredient and the curing agent weremixed uniformly together for evaluation of recovery ratio and thin-layercurability. Recovery ratio was, in the same manner as described above,measured by stretching a dumbbell-shaped cured article to 100%, fixingat 90° C. for 24 hours, then released at 23° C., whereby the recoveryratio was determined from the ratio that the token line had recoveredafter 1 hour.

Thin-layer curability was evaluated in the following manner. Theabove-described main ingredient and curing agent were weighed out, andmixed under stirring for 3 minutes using a spatula. The resultingmixture was placed onto an anodized aluminum (manufactured byEngineering Test Services Co., Ltd., measuring 0.8×70×150 mm) whichconformed to JIS H4000. An applicator was used to prepare a 25 μmthin-layer. This thin-layer was immediately placed into a 50° C. dryer.After 1 day, the thin-layer portion of the sealant was touched with thefinger to observe whether curing had occurred or not.

The recovery ratios of Example 28 and Example 29 were both high atrespectively 90% and 92%. Moreover, Example 28 exhibited good thin-layercurability.

Synthesis Example 13

An allyl-terminated polyisobutylene obtained in accordance with thepreparation examples described in Japanese Patent Publication No.11-209639 was reacted with triethoxysilane in the presence of a Ptcatalyst, to thereby obtain polyisobutylene (A-13) having triethoxysilylgroups on its terminals.

Synthesis Example 14

The allyl-terminated polyisobutylene obtained in Synthesis Example 13was reacted with methyldimethoxysilane in the presence of a Pt catalyst,to thereby obtain polyisobutylene (A-14) having methyldimethoxysilylgroups on its terminals.

Example 30 and Comparative Example 17

In relation to 100 parts by weight of the reactive silicongroup-containing organic polymers (A-13 and A-14) obtained in SynthesisExamples 13 and 14, 2 parts by weight of dibutyltin bisacetylacetonate(manufactured by Nitto Kasei Co., Ltd. under the trade name of NeostannU-220) was added to thereby obtain a cured article. The article in whichA-13 was used as the organic polymer was taken as Example 30, while thearticle in which A-14 was used as the organic polymer was taken asComparative Example 17. The cured article of Example 30 exhibited ahigher recovery ratio than that of Comparative Example 17.

Synthesis Example 15

CuBr (4.2 g) and acetonitrile (27.3 g) were charged into a reactionvessel equipped with a stirrer, and stirred at 65° C. for 15 minutesunder a nitrogen atmosphere. Added to the resultant mixture weren-butylacrylate (100 g), diethyl 2,5-dibromoadipate (8.8 g) andacetonitrile (16.6 g), and this mixture was thoroughly stirred.Pentamethyldiethylenetriamine (0.17) was added to the resultant mixtureto initiate polymerization. While stirring under heat at 70° C., n-butylacrylate (400 g) was continuously dropped. During the n-butyl acrylatedropping, triamine (0.68 g) was dropped divided in some portions.

When the monomer reaction ratio had reached 96%, the residual monomerand acetonitrile were evaporated off at 80° C., then 1,7-octadiene (53.7g), acetonitrile (132 g) and triamine (1.69 g) were charged therein. Theresulting mixture was subsequently stirred under heat at 70° C., tothereby obtain a mixture containing a polymer having alkenyl groups.

The acetonitrile and unreacted 1,7-octadiene in the mixture wereevaporated away under heat, and the resulting mixture was diluted withmethylcyclohexane. Undissolved polymer catalyst was made to precipitateusing a centrifugal separator and removed. An absorbent in the amount of6 parts absorbent (3 parts of KYOWAAD 500SH to 3 parts of KYOWAAD 700SL;both manufactured by Kyowa Chemical Industry Co., Ltd.) per 100 parts ofpolymer was added into a methylcyclohexane solution of the polymer andthe resultant solution was stirred under heat in an oxygen-nitrogen gasatmosphere. Undissolved portions were removed and the polymer solutionwas concentrated to thereby obtain a polymer (polymer [P1]) havingalkenyl groups.

The obtained polymer [P1] was evaporated off under heat (reducedpressure of 10 torr or less) while stirring at 180° C. for 12 hours, and100 parts of the resultant polymer were diluted with 400 parts ofmethylcyclohexane. After the formed solid portion was removed, thesolution was concentrated to thereby obtain polymer [P2]. Polymer [P2]had a number average molecular weight of 24,800 and a moleculardistribution of 1.36. The number of introduced alkenyl groups per 1polymer molecule was 1.8.

To this polymer [P2] were added and mixed in order methyl orthoformate(1 mole equivalent per alkenyl group), a platinum catalyst (10 mg per 1kg of polymer as the platinum metal amount) and1-(2-trimethoxysilylethynyl)-1,1,3,3-tetramethyldisiloxane (1.5 moleequivalent per alkenyl group). This mixture was stirred under heat undera nitrogen atmosphere at 100° C. for 0.5 hours. The fact that thealkenyl groups had been eliminated by the reaction was confirmed by¹H-NMR. The reaction mixture was concentrated to thereby obtain thedesired polymer (A-15), which contained trimethoxysilyl groups. Thenumber average molecular weight was 27,900 and molecular distributionwas 1.32. The number of introduced silyl groups per 1 polymer moleculewas 1.7.

Synthesis Example 16

A triethoxysilyl-group-containing polymer (A-16) was prepared in thesame manner as in Synthesis Example 15, except that triethoxysilane (3mole equivalent per alkenyl group) was used in place of the1-(2-trimethoxysilylethynyl)-1,1,3,3-tetramethyldisiloxane used inSynthesis Example 15 for the polymer [P2] obtained in Synthesis Example15. The number average molecular weight was 28,600 and moleculardistribution was 1.48. The number of introduced silyl groups per 1polymer molecule was 1.5.

Synthesis Example 17

A methyldimethoxysilyl-group-containing polymer (A-17) was prepared inthe same manner as in Synthesis Example 15, except thatmethyldimethoxysilane (3 mole equivalent per alkenyl group) was used inplace of the 1-(2-trimethoxysilylethynyl)-1,1,3,3-tetramethyldisiloxaneused in Synthesis Example 15 for the polymer [P2] obtained in SynthesisExample 15. The number average molecular weight was 28,400 and moleculardistribution was 1.51. The number of introduced silyl groups per 1polymer molecule was 1.5.

Examples 31 to 34 and Comparative Example 18

Added in relation to 100 parts by weight of an organic polymer having areactive silicon group were 150 parts by weight of surface-treatedprecipitated calcium carbonate (manufactured by Shiraishi Kogyo Co.,Ltd. under the trade name of HAKUENKA CCR), 20 parts by weight of groundcalcium carbonate (manufactured by Maruo Calcium Co., Ltd., under thetrade name of NANOX 25A), 10 parts by weight of titanium oxide(manufactured by Ishihara Sangyo Kaisha, Ltd., under the trade name ofTipaque R-820), 60 parts by weight of a plasticizer diisodecyl phthalate(manufactured by New Japan Chemical Co., Ltd., under the trade nameSANSOCIZER DIDP), 2 parts by weight of a thixotropy imparting agent(manufactured by Kusumoto Chemicals, Ltd., under the trade nameDisparlon 6500), 1 part by weight of a photostabilizer (manufactured bySankyo Co., Ltd. under the trade name of Sanol LS-765), 1 part by weightof an ultraviolet absorber (manufactured by Ciba Specialty Chemicals,under the trade name of TINUVIN 213), 2 parts by weight of thedehydrating agent vinyltrimethoxysilane (manufactured by Nippon UnicarCo., Ltd. under the trade name of A-171), 2 parts by weight of anadhesion-imparting agent N-(β-aminoethyl)-γ-aminopropyltrimethoxysilane(manufactured by Nippon Unicar Co., Ltd. under the trade name ofA-1120), and as the curing catalyst, 0.2 parts by weight of dibutyltinbisacetylacetonate (manufactured by Nitto Kasei Co., Ltd. under thetrade name of Neostann U-220). The resultant mixture was kneaded underdehydrating conditions in a state in which the mixture was essentiallyfree from water, then sealed into a moisture-proof container to obtain aone-part curable composition. As the organic polymer having a reactivesilicon group, Example 31 used 100 parts by weight of the acrylic esterpolymer (A-15) having a trimethoxysilyl group obtained in SynthesisExample 15; Example 32 used a 100 parts by weight mixture consisting of50 parts by weight of (A-15) and 50 parts by weight of thepolyoxypropylene polymer (A-4) having a methyldimethoxysilyl groupobtained in Synthesis Example 4; Example 33 used 100 parts by weight ofthe acrylic ester polymer (A-16) having a triethoxysilyl group obtainedin Synthesis Example 16; Example 34 used a 100 parts by weight mixtureconsisting of 50 parts by weight of (A-16) and 50 parts by weight of thepolyoxypropylene polymer (A-3) having a triethoxysilyl group obtained inSynthesis Example 3; and Comparative Example 18 used a 100 parts byweight of the acrylic ester polymer (A-17) having a methyldimethoxysilylgroup obtained in Synthesis Example 17. The cured articles of Examples31 to 34 exhibited a higher recovery ratio than that of ComparativeExample 18.

1. A curable composition comprising: an organic polymer (A1) having oneor more silicon-containing functional groups capable of cross-linking byforming siloxane bonds in which the one or more silicon-containingfunctional groups capable of cross-linking by forming siloxane bonds aresilicon-containing functional groups each having three or morehydrolyzable groups on one or more silicon atoms thereof; and acomponent which is selected from the group consisting of (a) a silicate(B), (b) a tin carboxylate (C1) in which the α-carbon of the carboxylgroup is a quaternary carbon atom, (c) a tin carboxylate (C) and anorganotin catalyst (D), (d) a non-tin catalyst (E), and (e) amicroballoon (F).
 2. The curable composition according to claim 1,wherein the component is component (a) and the silicate (B) is acondensate of a tetraalkoxysilane.
 3. The curable composition accordingto claim 1, wherein the component is component (a) and furthercomprising a tin carboxylate (C).
 4. A curable composition according toclaim 1, wherein the component is component (b).
 5. A curablecomposition according to claim 1, wherein the component is component(c).
 6. A curable composition according to claim 1, wherein thecomponents is component (d).
 7. The curable composition according toclaim 6, wherein the non-tin catalyst is one or more selected from acarboxylic acid, a metal carboxylate other than a tin carboxylate and anorganic titanate.
 8. The curable composition according to claim 6,wherein the non-tin catalyst is a catalyst which comprises a carboxylicacid and an amine compound.
 9. The curable composition according toclaim 7 or 8, wherein the carboxylic acid is a carboxylic acid in whichthe α-carbon atom of the carboxyl group is a quaternary carbon atom. 10.A curable composition according to claim 1, wherein the component iscomponent (e).
 11. A curable composition characterized comprising: anorganic polymer (A1) having one or more silicon-containing functionalgroups capable of cross-linking by forming siloxane bonds in which theone or more silicon-containing functional groups capable ofcross-linking by forming siloxane bonds are silicon-containingfunctional groups each having three or more hydrolyzable groups, on oneor more silicon atoms thereof, and the proportion of said organicpolymer in the total amount of the curable composition being 5 to 28 wt%.
 12. The curable composition according to claim 1 or 11, wherein theorganic polymer having one or more silicon-containing functional groupscapable of cross-linking by forming siloxane bonds is an organic polymerobtained by an addition reaction between an organic polymer having oneor more unsaturated groups introduced into the terminals thereof and ahydrosilane compound represented by the general formula (1):H—SiX₃  (1) where X represents a hydroxy group or a hydrolyzable group,and three X's may be the same or different.
 13. The curable compositionaccording to claim 1 or 11, wherein the one or more silicon-containingfunctional groups capable of cross-linking by forming siloxane bondseach are a trimethoxysilyl group or a triethoxysilyl group.
 14. Thecurable composition according to claim 1, wherein the one or moresilicon-containing functional groups capable of cross-linking by formingsiloxane bonds each are a group represented by the general formula (2):—Si(OR¹)₃  (2) where three R¹s each are independently a monovalentorganic group having 2 to 20 carbon atoms.
 15. A curable compositioncomprising: an organic polymer (A2) having one or moresilicon-containing functional groups capable of cross-linking by formingsiloxane bonds in which the one or more silicon-containing functionalgroups capable of cross-linking by forming siloxane bonds arerepresented by the general formula (2):—Si(OR¹)₃  (2) where three R¹s each are independently a monovalentorganic group having 2 to 20 carbon atoms; and a component which isselected from the group consisting of (a) an aminosilane coupling agent(G) having a group represented by the general formula (3):—SiR² a(OR³)_(3-a)  (3) where a R²s each are independently a monovalentorganic group having 1 to 20 carbon atoms, (3-a) R³s each areindependently a monovalent organic group having 2 to 20 carbon atoms,and a represents 0, 1 or 2 and (b) an epoxy resin.
 16. A curablecomposition obtained by aging a composition comprising: an organicpolymer (A2) having one or more silicon-containing functional groupscapable of cross-linking by forming siloxane bonds in which the one ormore silicon-containing functional groups capable of cross-linking byforming siloxane bonds are represented by the general formula (2):—Si(OR¹)₃  (2) where three R¹s each are independently a monovalentorganic group having 2 to 20 carbon atoms; and an aminosilane couplingagent (H) having a group represented by the general formula (4):—SiR⁴ b(OCH³)c(OR⁵)_(3-b-c)  (4) where b R⁴s each are independently amonovalent organic group having 1 to 20 carbon atoms, (3-b-c) R⁵s eachare independently a monovalent organic group having 2 to 20 carbonatoms, b represents 0, 1 or 2, and c represents 1, 2 or 3; the relation,3-b-c≧0, is to be satisfied.
 17. A curable composition according toclaim 15, wherein the component is component (b).
 18. A curablecomposition comprising a polyoxyalkylene polymer (A3) having one or moresilicon-containing functional groups capable of cross-linking by formingsiloxane bonds in which the one or more silicon-containing functionalgroups capable of cross-linking by forming siloxane bonds arerepresented by the general formula (2):—Si(OR¹)₃  (2) where three R¹s each are independently a monovalentorganic group having 2 to 20 carbon atoms; and a (meth)acrylatecopolymer (A4) having one or more silicon-containing functional groupscapable of cross-linking by forming siloxane bonds.
 19. The curablecomposition according to claim 18, wherein the one or moresilicon-containing functional groups of the (meth)acrylate copolymer arethe groups represented by the general formula (2):—Si(OR¹)₃  (2) where three R¹'s each are independently a monovalentorganic group having 2 to 20 carbon atoms.
 20. A curable compositioncomprising a saturated hydrocarbon polymer (A5) having one or moresilicon-containing functional groups capable of cross-linking by formingsiloxane bonds in which the one or more silicon-containing functionalgroups capable of cross-linking by forming siloxane bonds arerepresented by the general formula (2):—Si(OR¹)₃  (2) where three R's each are independently a monovalentorganic group having 2 to 20 carbon atoms.
 21. A curable compositioncomprising a (meth)acrylate copolymer (A6) having one or moresilicon-containing functional groups capable of cross-linking by formingsiloxane bonds in which the one or more silicon-containing functionalgroups capable of cross-linking by forming siloxane bonds arerepresented by the general formula (2):—Si(OR¹)₃  (2) where three R¹s each are independently a monovalentorganic group having 2 to 20 carbon atoms.
 22. The curable compositionaccording to any one of claims 14, 15, 16, 18, 20 and 21, wherein theorganic polymer having one or more silicon-containing functional groupscapable of cross-linking by forming siloxane bonds is an organic polymerobtained by an addition reaction between an organic polymer having oneor more unsaturated groups introduced into the terminals thereof and ahydrosilane compound represented by the general formula (5):H—Si(OR¹)₃  (5) where three R¹s each are independently a monovalentorganic group having 2 to 20 carbon atoms.
 23. The curable compositionaccording to any one of claims 1, 11, 15, 16, 18, 20 and 21, wherein theorganic polymer having one or more silicon-containing functional groupscapable of cross-linking by forming siloxane bonds is an organic polymerwhich substantially does not contain an amide segment (—NH—CO—) in themain chain skeleton thereof.
 24. The curable composition according toany one of claims 1, 11, 15, 16, 18, 20 and 21, wherein the one or moresilicon-containing functional groups capable of cross-linking by formingsiloxane bonds each are a triethoxysilyl group.
 25. The curablecomposition according to any one of claims 1, 11, 17, 18, 20 and 21,further comprising an aminosilane coupling agent.
 26. A one-part curablecomposition according to any one of claims 1, 11, 15, 16, 18, 20 and 21,further comprising a dehydrating agent. 27-76. (canceled)
 77. Thecurable composition according to claim 1, wherein the component iscomponent (a).
 78. The curable composition according to claim 15,wherein the component is component (a).
 79. The curable compositionaccording to claim 14, wherein the one or more silicon-containingfunctional groups capable of cross-linking by forming siloxane bondseach are a group represented by the general formula (2):—Si(OR¹)₃  (2) where three R¹s each are independently a monovalentorganic group having 2 to 20 carbon atoms.
 80. The curable compositionaccording to claim 79, wherein the organic polymer having one or moresilicon-containing functional groups capable of cross-linking by formingsiloxane bonds is an organic polymer obtained by an addition reactionbetween an organic polymer having one or more unsaturated groupsintroduced into the terminals thereof and a hydrosilane compoundrepresented by the general formula (5):H—Si(OR¹)₃  (5) where three R¹s each are independently a monovalentorganic group having 2 to 20 carbon atoms.